CN103926795A - Photocurable Composition - Google Patents

Abstract

The invention provides a photocurable composition, a cured object of the photocurable composition, an optical equipment component with the cured object, a set of optical equipment, and a manufacturing method of a display module with the photocurable composition. The photocurable composition has excellent thermal creep resistance, excellent operability, excellent durability and excellent binding performance. Furthermore thick film of the photocurable composition can be cured. The solution of the photocurable composition is characterized in that the photocurable composition comprises the components of: (A) a (methyl)acrylate series polymer with more than 0.8 crossed organosilyl in one molecule, (B) a composition of the (methyl)acrylate series group comprising the (methyl)acrylate series group represented by a general formula (1), (C) a curing catalyst, (F) an optical free radial and (I) a resin filler with an average particle diameter of 1-150 mu m. -OC(O)C(R1)=CH2...(1) (wherein in the general formula (1), R1 represents a hydrogen atom or an organic group with number of carbon atoms in 1-20.).

Description

Photocurable composition

Technical field

The manufacture method that the present invention relates to the solidfied material of Photocurable composition, this Photocurable composition, the optical device member, the optical device that contain this solidfied material, uses the display module of this Photocurable composition.Photocurable composition of the present invention is as optical device, particularly as the sealer of liquid crystal display, can be aptly for the purposes that enters of the leakage of fixing, prevent light backlight of the optical material parts such as liquid crystal panel, anti-outer light.

Background technology

In recent years, be accompanied by the high performance of the displays such as liquid crystal display or optical lens, optical pick-up, sensor optoelectronic device, in order to realize, maintain high sensitivity, must make the loss of passing through from member, fixing resin layer, cause from outside transmitted light, from inner light leak, from the light leak in space reduce, particularly, requiring as fixing resin layer in the part of the various characteristicses such as cementability or cohesive, intensity, permanance, moisture-proof, same resin need to have these characteristics and shading concurrently.

In order to reach above-mentioned requirements, patent documentation 1 discloses a kind of Photocurable resin composition, its by utilize matrix resin light-cured resin solidfied material and therein add compound between refringence, utilize light effectively to solidify, even if the resin that therefore thickness is thicker also can solidify, the transmittance of the cured resin of gained is low.

In addition, present situation is that uncured cohesive film stamping-out is processed as frame shape by use conventionally, fits in after glass substrate, makes the curing method of film.

When sealers using Photocurable resin composition as liquid crystal display etc. use, on substrate etc., form after Photocurable resin composition with frame shape, enforcement is solidified light-cured resin, by the operation of the bonding bonded object of Photocurable resin composition (liquid crystal panel).Herein, for uses such as the sealers using the Photocurable resin composition of recording in patent documentation 1 as liquid crystal display, in Photocurable resin composition, coordinate thermoset resin, seek the Photocurable resin composition after photocuring to give cementability.Therefore, except the operation of photocuring, also need the operation of heat curing, the operation of this heat curing needs long-time.In addition, in the parts of liquid crystal display, be sometimes included in the parts of approximately 70 DEG C of distortion, now, in the heat curing operation of Photocurable resin composition, the problem that has the parts of liquid crystal display to be out of shape.

In addition, be processed as in the method for cohesive film of frame shape in use, have following problems: the stamping-out width limit of film is about 0.5mm, and high-density installationization is limited, in addition, because being created in the membrane portions not using after stamping-out, therefore finished material rate is low.

In addition, be processed as in the method for film of frame shape in use, because of the processing trouble of the film after processing, further, the mechanization difficulty of the bonding process of film, therefore present situation is to carry out the laminating of film by labour's manual operations, has the problem of the robotization difficulty of production line.

In order to eliminate the problems referred to above, in patent documentation 2, recorded a kind of Photocurable resin composition, it contains: (A) light-cured resin, (B) tackifier, (C) have with this (A) composition and (B) specific refractivity of the solidfied material of composition be more than 0.01 refractive index, with respect to this (A) composition and (B) composition be incompatibility and there is dispersed compound and (D) black pigment.But there is the inadequate problem points of cementability in the Photocurable resin composition of recording in patent documentation 2.

In addition, because of the heat-resisting creep properties of bonding agent in the past poor, because the heat producing in summer or while using causes flowing, therefore there is producing the problem of skew.In addition, need area to a certain degree in order to eliminate skew, have to make shadow shield (ベ ゼ Le) part chap, occurred the problem of designability variation.There is in recent years wanting the demand that shadow shield part is attenuated.In addition, in the past, large-scale, there is the problem of easy generation strain in more than 47 cun liquid crystal display for example.

Prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2007-119684 communique

Patent documentation 2: TOHKEMY 2010-126630 communique

Summary of the invention

The problem that invention will solve

The object of this invention is to provide heat-resisting creep properties, workability, permanance and excellent in adhesion, can thick film curing Photocurable composition, the solidfied material of this Photocurable composition, the optical device member, the optical device that contain this solidfied material, the manufacture method that uses the display module of this Photocurable composition.

The means of dealing with problems

In order to address the above problem, Photocurable composition of the present invention is characterised in that, it contains: what (methyl) acrylic ester polymer, (B) (A) on average in 1 molecule with more than 0.8 bridging property silicyl had the group shown in following general formula (1) (in the present invention this group being called to (methyl) acryloyl is base) is the compound, (C) curing accelerator, (F) optical free radical initiating agent of base and (I) resin extender of mean grain size 1～150 μ m containing (methyl) acryloyl.

-OC（O）C（R ¹）=CH ₂···（1）

(in described general formula (1), R ¹represent the organic group of hydrogen atom or carbon number 1～20)

It should be noted that, in the present invention methacrylic acid and acrylic acid are referred to as to (methyl) acrylic acid, methacryl and acryloyl group are referred to as to (methyl) acryloyl group.

In Photocurable composition of the present invention, utilize following mathematical expression (1) the OD value that the transmissivity under 400～800nm wavelength calculates by the solidfied material of the Photocurable composition of thickness 1000 μ m to be preferably more than 2.5.

OD value=-log ₁₀t(1)

(in described mathematical expression (1), T represents the transmissivity (%) of each wavelength.）

Described (I) resin extender should comprise the resin extender of black.

Described (B) containing (methyl) acryloyl be the compound of base be preferably be selected from (P) main chain be not polysiloxane be the organic polymer of base containing (methyl) acryloyl, (D) there is (methyl) acrylate monomer of alkyl, (E) have polar group containing (methyl) acryloyl be the monomer of base, (G) 1 or 2 functionalities have phosphate containing (methyl) acryloyl be the monomer of base and (H) multi-functional containing (methyl) acryloyl be the monomer of base multi-functional containing (methyl) acryloyl be in the monomer of base more than a kind.

Described (C) curing accelerator is preferably photoacid generator.

As described photoacid generator, can use be aptly selected from sulfosalt and salt compounded of iodine more than a kind.

In addition, described photoacid generator preferably has and is selected from (R ¹¹sO ₂) ₂n ^-, (R ¹¹sO ₂) ₃c ^-, R ¹¹sO ₃ ^-and PF ₆ ^-in a kind of above negative ion (R herein, ¹¹represent alkyl, the perfluoroalkyl of carbon number 1～20 or the aryl of carbon number 6～20 of carbon number 1～20, alkyl and perfluoroalkyl can be any in straight chain, a chain or ring-type, and aryl can be unsubstituted, also can have substituting group.) as counter anion, from the viewpoint of more preferably (R of this negative ion of cementability ¹¹sO ₂) ₂n ^-, (R ¹¹sO ₂) ₃c ^-or R ¹¹sO ₃ ^-.

The Tg of described (I) resin extender is preferably 20 DEG C～-60 DEG C, more preferably 0 DEG C～-50 DEG C.

Photocurable composition of the present invention preferably also contains (J) moisture absorber.

Photocurable composition of the present invention preferably also contains (K) light-proofness material.

Solidfied material of the present invention is the solidfied material of Photocurable composition of the present invention.

Optical device member of the present invention is characterised in that and contains solidfied material of the present invention.

Optical device of the present invention is characterised in that and comprises optical device member of the present invention.

As this optical device, for example, display module is preferred.

The manufacture method of display module of the present invention is characterised in that and uses Photocurable composition of the present invention.

The manufacture method of display module of the present invention preferably includes: the operation that is coated with described Photocurable composition in the outer regions of the 1st member; To described applied Photocurable composition light irradiation, the 1st curing process that the compound that makes described (B) be base containing (methyl) acryloyl solidifies; After described the 1st curing process, the 2nd member is engaged in to the fit operation of display module of described the 1st member; After described bonding process, utilize the moisture curing of described (A) polymkeric substance to make described the 1st member and the bonding curing operation of the 2nd member.

Invention effect

Because there is UV retardation of curing in Photocurable composition of the present invention, utilize light and gelation showing after initial cementability, temporary transient fixing, afterwards, by utilize moisture the 2nd solidify carry out bonding, therefore have can the 2nd solidify before fit and can be offset recovery, workability, excellent in te pins of durability, heat-resisting creep properties excellence, even also stable effect at high temperature.Because the present invention can eliminate the problem of strain, therefore be specially adapted to large-scale display module.

In addition, Photocurable composition of the present invention can be lower curing at normal temperature (room temperature).Further, Photocurable composition energy thick film of the present invention solidifies.

Further, the present invention can also reach excellent light-proofness and adhesion durability.In the past, need to be for black in order to obtain light-proofness, but occurred that thick film solidifies the problem of variation while making black.Even also can solidify by thick film in the situation that the present invention having light-proofness making black.

Because Photocurable composition of the present invention can solidify effectively therefore can thick film solidify, the transmitance from inside to outside of the solidfied material of gained is low, and light-proofness is high, cohesive excellence, and the various characteristics such as intensity, permanance, moisture-proof is also excellent.In addition, because Photocurable composition of the present invention can print, coating etc., therefore not only the utilization rate of Photocurable composition is high, and the formation of microfine circuit is easy, and further, the robotization of production line energy, therefore can make productive rate significantly improve.Therefore, Photocurable composition of the present invention, preferably as bonding agent, sealer, coating agent, is suitable as the sealer of optical device, particularly liquid crystal display especially.

Brief description of the drawings

Fig. 1 is the schematic diagram that shows an example of the manufacture method of display module of the present invention, (a) represents the operation of coating Photocurable composition, the operation that (b) represents to utilize light-struck the 1st curing process and (c) represent laminating display module.

Label declaration

10: display module

12: Photocurable composition

14: bonding coat

16: adhesive linkage

18: interior zone

20: spreader

22: back light unit

24: ultraviolet lamp

26: liquid crystal panel

W: width dimensions

Embodiment

Below embodiments of the present invention are described, but from needless to say these are only to illustrate, only otherwise departing from technological thought of the present invention just can carry out various distortion.

Photocurable composition of the present invention contains following compositions (A), (B), (C), (F) and (I).

(A) in 1 molecule, on average have more than 0.8 bridging property silicyl (methyl) acrylic ester polymer,

(B) have (methyl) acryloyl shown in following general formula (1) be base containing (methyl) acryloyl be base compound,

(C) curing accelerator,

(F) optical free radical initiating agent and

(I) resin extender of mean grain size 1～150 μ m.

In 1 molecule, on average have in (methyl) acrylic ester polymer of more than 0.8 bridging property silicyl at above-mentioned (A), can list the group shown in following formula (2) as bridging property silicyl.

-[Si（R ²） _2-b（Y） _bO] _m-Si（R ³） _3-a（Y） _a···（2）

In above-mentioned formula (2), R ²and R ³identical or different, represent the alkyl of carbon number 1～20, the aryl of carbon number 6～20, aralkyl or (R ') of carbon number 7～20 ₃represented three organosiloxies of SiO-(in formula, the alkyl of 1 valency of R ' expression carbon number 1～20.Multiple R ' can be identical also can be different).There is respectively more than two R ²or R ³time, they can be identical also can be different.Y represents hydroxyl or hydrolization group.Exist when more than two Y, they can be identical also can be different.A represents 0,1,2 or 3.B represents 0,1 or 2.M represents 0～19 integer.But, meet a+mb >=1.

Y is as hydrolization group, can enumerate as normally used groups such as hydrogen atom, alkoxy, acyloxy, ketoxime base, amino, amide group, aminooxy group, sulfydryl, alkene oxygen bases.Among them, preferably alkoxy, amide group, aminooxy group, but from the viewpoint of water-disintegrable gentleness and easily processing, particularly preferably alkoxy.

The number of the bridging property silicyl in above-mentioned (A) (methyl) acrylic ester polymer average out in 1 molecule more than 0.8, is preferably 1～5, more preferably 1.3～3.Bridging property silicyl can be in side chain or molecular end arbitrary place, but preferably in molecular end.

(methyl) acrylic ester monomer of the raw material of above-mentioned as becoming (A) (methyl) acrylic ester polymer, can enumerate as (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid n-pentyl ester, the just own ester of (methyl) acrylic acid, (methyl) cyclohexyl acrylate, the positive heptyl ester of (methyl) acrylic acid, (methyl) acrylic acid n-octyl, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) phenyl acrylate, (methyl) acrylic acid toluyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid-2-methoxyl ethyl ester, (methyl) acrylic acid-3-methoxyl butyl ester, (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) stearyl acrylate ester, (methyl) glycidyl acrylate, (methyl) acrylic acid-2-amino ethyl ester, γ-(methacryloxy) propyl trimethoxy silicane, (methyl) acrylic acid ethylene oxide adduct, (methyl) acrylic acid trifluoromethyl methyl esters, (methyl) acrylic acid-2-trifluoromethyl ethyl ester, (methyl) acrylic acid-2-perfluor diethyl acetamidomalonate, (methyl) acrylic acid-2-perfluor ethyl-2-perfluoro butyl ethyl ester, (methyl) acrylic acid 2-perfluor ethyl ester, (methyl) acrylic acid perfluor methyl esters, (methyl) acrylic acid two perfluoro-methyl methyl esters, (methyl) acrylic acid-2-perfluoro-methyl-2-perfluor diethyl acetamidomalonate, (methyl) acrylic acid-2-perfluoro hexyl ethyl ester, (methyl) acrylic acid-2-perfluor decyl ethyl ester, (methyl) acrylic acid-2-perfluor cetyl ethyl ester etc.They can be used alone and also can use by multiple combination.

In the present invention, with regard to above-mentioned (A) (methyl) acrylic ester polymer, except making (methyl) acrylic ester monomer polymerization, also can make as required other monomer copolymerizations, now, preferably contain by quality ratio more than 40% (methyl) acrylic ester monomer.

As above-mentioned other monomers, preferred other ethene base system monomers, can enumerate as aromatic vinyl base system monomers such as styrene, vinyltoluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and salt thereof; The fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropene, vinylidene fluoride; The ethene base system monomer that vinyltrimethoxy silane, vinyltriethoxysilane etc. are siliceous; The mono alkyl ester of maleic anhydride, maleic acid, maleic acid and dialkyl; The mono alkyl ester of fumaric acid, fumaric acid and dialkyl; The maleimides such as maleimide, methyl maleimide, ethyl maleimide, propyl group maleimide, butyl maleimide, hexyl maleimide, octyl group maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, N-cyclohexylmaleimide are monomer; The ethene base system monomer of the nitrile group-containing such as vinyl cyanide, methacrylonitrile; The ethene base system monomer of the amide-containing such as acrylamide, Methacrylamide; The vinyl esters such as vinyl acetate, propionate, pivalic acid vinyl acetate, vinyl benzoate, vinyl cinnamate; The olefines such as ethene, propylene; Butadiene, isoprene equiconjugate dienes; Vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol etc.

The molecular weight distribution (the matter average molecular weight (Mw) of measuring with gel permeation chromatography (GPC) and the ratio of number-average molecular weight (Mn)) of above-mentioned (A) (methyl) acrylic ester polymer is not particularly limited, but be preferably less than 1.8, more preferably below 1.7, more preferably below 1.6, be particularly preferably below 1.5, especially be preferably below 1.4, most preferably be below 1.3.

It should be noted that, when GPC in the present invention measures, conventionally, using chloroform or tetrahydrofuran as mobile phase, use Aquapak A-440 post, obtain the value of molecular weight with the form of polystyrene conversion value.

The lower limit of the number-average molecular weight of above-mentioned (A) (methyl) acrylic ester polymer is preferably 500, and more preferably 3,000, the upper limit is preferably 100,000, and more preferably 40,000.If molecular weight less than 500, has and become the tendency that is difficult to show the original characteristic of polymkeric substance, if exceed 100,000, have to process easily to become difficult tendency.

Manufacture method about above-mentioned (A) (methyl) acrylic ester polymer is not particularly limited, but preferably by anionic polymerisation or the incompatible manufacture of radical polymerization, considers more preferably free radical polymerization from the versatility of monomer or the easness of control.In free radical polymerization, preferably by active free radical polymerization or used the incompatible manufacture of radical polymerization of chain-transferring agent, more preferably living radical polymerization, particularly preferably Transfer Radical Polymerization.

(polymerization)

The manufacture radical polymerization used of above-mentioned (A) (methyl) acrylic ester polymer can be divided into: use azo based compound, superoxide etc. as polymerization initiator, make to have the monomer of specific functional group and ethene base system monomer carries out merely " the common radical polymerization " of copolymerization and can wait endways controlled position to import " the controllable free-radical polymerisation method " of specific functional group.

" common radical polymerization " is easy method, but because the method can only import the monomer with specific functional group randomly in polymkeric substance, therefore in the time going for the high polymkeric substance of sense rate, need to use quite in large quantities this monomer, otherwise if having a small amount of ratio that uses the polymkeric substance that does not import this specific functional group to become large problem.In addition, because be free radical polymerization, therefore can only obtain in addition the problem of the wide and polymkeric substance that viscosity is high of molecular weight distribution.

" controllable free-radical polymerisation method " can further be categorized as: the chain-transferring agent that has a specific functional group by use carries out polymerization and had endways " the chain-transferring agent method " of the vinyl based polymer of functional group; With do not cause ground such as stopping reaction grow " living radical polymerization " of the polymkeric substance that obtains the designed the same molecular weight of making peace greatly by aggregation growth end.

" chain-transferring agent method " though can obtain official can rate high polymkeric substance, need to be with respect to quite a large amount of chain-transferring agent with specific functional group of initiating agent, comprise processing having problems in internal economy aspect.In addition, same with above-mentioned " common radical polymerization ", therefore because be that free radical polymerization exists the problem that can only obtain the polymkeric substance that molecular weight distribution is wide, viscosity is high.

Different from these polymerizations, " living radical polymerization " is although so be considered to stop the unmanageable free radical polymerization of reaction due to what polymerization speed soon, easily caused that free radical coupling each other etc. causes, but, its be difficult for causing stop reaction, in obtaining (Mw/Mn is 1.1～1.5 left and right) polymkeric substance of narrow molecular weight distribution, can freely control molecular weight by the rate of charge of monomer and initiating agent.

Therefore, " living radical polymerization " not only can obtain narrow molecular weight distribution, polymkeric substance that viscosity is low, and can import the monomer with specific functional group in the almost optional position of polymkeric substance, therefore its manufacture method as the above-mentioned vinyl based polymer with specific functional group is more preferred.

It should be noted that, thereby living polymerization narrowly refers to that end continues to have the polymerization that activity strand is grown down all the time, conventionally also comprise the accurate living polymerization that the material that end is passivated and the material being activated are grown down in the time of equilibrium state.Definition in the present invention is also the latter.

Various organizing energetically carried out and studied " living radical polymerization " in recent years.As its example, can enumerate as: use at JournaloftheAmericanChemicalSociety(J.Am.Chem.Soc.), 1994,116 volumes, the method for the such cobalt porphyrin complex shown in 7943 pages; Use at the large molecule of Macromolecules(), 1994,27 volumes, the method for the free radical scavengers such as the such oxides of nitrogen shown in 7228 pages; Using organohalogen compounds etc. as initiating agent " atom transfer radical polymerization " using transition metal complex as catalyzer (Atom Transfer Radical Polymerization:ATRP) etc.

At " in living radical polymerization "; using organohalogen compounds or halogenation sulfonyl compound etc. as initiating agent, " Transfer Radical Polymerization " of using transition metal complex as catalyzer, ethene base system monomer being carried out to polymerization; except the feature of above-mentioned " living radical polymerization "; because thering is endways halogen relatively favourable in functional group's conversion reaction etc.; the design freedom of initiating agent or catalyzer is large, therefore further preferably conduct has the manufacture method of the vinyl based polymer of specific functional group.

As above-mentioned Transfer Radical Polymerization, can enumerate as at Matyjaszewski people etc., JournaloftheAmericanChemicalSociety(J.Am.Chem.Soc.) nineteen ninety-five, 117 volumes, 5614 pages; The large molecule of Macromolecules() nineteen ninety-five, 28 volumes, 7901 pages, Science(science) 1996 years, 272 volumes, 866 pages; WO96/30421 pamphlet; WO97/18247 pamphlet or Sawamoto people etc., the large molecule of Macromolecules() nineteen ninety-five, 28 volumes, the method for recording in 1721 pages etc.

In the present invention, use which kind of method among these to there is no special restriction, can radical polymerization processed but substantially utilize, further consider preferred living radical polymerization, particularly preferably Transfer Radical Polymerization from the easness controlled etc.

In atom transfer radical polymerization, as the transition metal complex as polymerization catalyst, though be not particularly limited, but can preferably list the transition metal complex of metal centered by ruthenium, the iron of divalent or the nickel of divalent of the copper of the copper of 0 valency, 1 valency, divalent, can particularly preferably enumerate the complex compound of copper.

(importing of functional group)

As above-mentioned in order to obtain (A) (methyl) though acrylic ester polymer and being not particularly limited to the method that polymkeric substance imports bridging property silicyl can enumerate as the method for record in TOHKEMY 2004-210858 communique paragraph [0102]～[0112].Easier from the viewpoint of controlling among these methods, preferably: the method that there is the hydrogen silylation of the hydrosilylation compound of bridging property silicyl, manufactures by the thiazolinyl of polymkeric substance with end thiazolinyl being transformed to the method for bridging property silicyl by utilization.

Above-mentioned (A) (methyl) acrylic ester polymer can be used alone and also can be used in combination.

Above-mentioned (B) is that the compound of base is that to have (methyl) acryloyl shown in following general formula (1) be the compound of base containing (methyl) acryloyl, can use any in monomer, oligomer and polymkeric substance.

-OC（O）C（R ¹）=CH ₂···（1）

In formula (1), R ¹represent the organic group of hydrogen atom or carbon number 1～20, be preferably replacement or the unsubstituted alkyl of hydrogen atom or carbon number 1～20.

As replacement or the unsubstituted alkyl of above-mentioned carbon number 1～20, can list the alkyl of carbon number 1～20, the aryl of carbon number 6～20, aralkyl, the itrile group etc. of carbon number 7～20, they can have the substituting groups such as hydroxyl.

As the alkyl of above-mentioned carbon number 1～20, can enumerate as methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, decyl etc.As the aryl of carbon number 6～20, can enumerate as phenyl, naphthyl etc.As the aralkyl of carbon number 7～20, can enumerate as benzyl, phenylethyl etc.

As R ¹concrete example, can enumerate as-H ,-CH ₃,-CH ₂cH ₃,-(CH ₂) _ncH ₃(n represents 2～19 integer) ,-C ₆h ₅,-CH ₂oH ,-CN etc.,, formula (1) is acryloxy to be preferably-H() ,-CH ₃(, formula (1) is methacryloxy).

While using oligomer or polymkeric substance to be the compound of base as above-mentioned (B) containing (methyl) acryloyl, preferably (P) main chain be not polysiloxane be the organic polymer of base containing (methyl) acryloyl.Use monomer as above-mentioned (B) containing (methyl) acryloyl while being the compound of base, (methyl) acrylate monomer, (E) that can preferably use (D) to there is alkyl have polar group containing (methyl) acryloyl be base monomer, (G) 1 or 2 functionalities have phosphate containing (methyl) acryloyl be monomer, (H) of base multi-functional be the monomer of base containing (methyl) acryloyl.They can be used alone or are used in combination.

Composition (B) though mixing ratio be not particularly limited, be preferably 10～300 mass parts with respect to composition (A) 100 mass parts, more preferably 20～180 mass parts.

(methyl) acryloyl in above-mentioned (P) organic polymer is the number of base, from making its crosslinked viewpoint consider that average out to more than 0.8, is preferably more than 11 molecule, and more preferably 1～5, more preferably 1.3～3.(methyl) acryloyl is arbitrary place that base can be in side chain or molecular end, but from making between crosslinking points molecular weight evenly and large, is preferably and makes 500～100000 and the viewpoint that obtains caoutchouc elasticity is considered, is preferably present in the molecular end of polymkeric substance.

The composition that forms the main chain of above-mentioned (P) organic polymer is just not particularly limited so long as not polysiloxane, can use oligomer and polymkeric substance, considers preferred vinyl based polymer, more preferably (methyl) acrylic acid series polymeric compounds from stable on heating viewpoint.

Above-mentioned as having (methyl) acryloyl is the vinyl based polymer of base, can use containing (methyl) acryloyl and be the ethene base system oligomer of base and be any in the vinyl based polymer of base containing (methyl) acryloyl.Becoming the above-mentioned ethene base system monomer that is the raw material of the vinyl based polymer of base containing (methyl) acryloyl is not particularly limited, for example, preferably use at the ethene base system monomer described in the explanation of above-mentioned (A) (methyl) acrylic ester polymer, (methyl) acrylic ester monomer.In addition, use the manufacture method of the vinyl based polymer of this monomer to be also not particularly limited, for example, preferably in the method described in the explanation of above-mentioned (A) (methyl) acrylic ester polymer.

Be the method for base as import (methyl) acryloyl in polymkeric substance, can utilize known method.Can enumerate the method for recording as in TOHKEMY 2004-203932 communique paragraph [0080]～[0091].Except these methods, have to make to there is isocyanate group and (methyl) acryloyl is the monomer and the method that (methyl) acrylic acid series polymeric compounds with C-terminal reacts of base, can enumerate as used 2-(methyl) method of acrylyl oxy-ethyl isocyanates etc.

In addition, have (methyl) acryloxy (methyl) acrylic acid series polymeric compounds, there is (methyl) acrylic acid series polymeric compounds of functional group, can use and import (methyl) acryloyl at side chain is the material of base.

In addition, as above-mentioned (P) organic polymer, can use polyester (methyl) acrylate, epoxy (methyl) acrylate, polyethers (methyl) acrylate and carbamate (methyl) acrylate oligomer etc. is the oligomer of base containing (methyl) acryloyl.

As polyester (methyl) acrylate oligomer, can list polyester polyol and (methyl) acrylic acid dehydration condensation etc.As polyester polyol, can list the reaction product of polyvalent alcohol and carboxylic acid or its acid anhydrides etc. herein.

As polyvalent alcohol, can list ethylene glycol, diethylene glycol, triethylene glycol, TEG, polyglycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, polytetramethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexanedimethanol, 3-methyl isophthalic acid, 5-pentanediol, 1, the low molecular weight polyols such as 6-hexanediol, trimethylolpropane, glycerine, pentaerythrite and dipentaerythritol and their alkylene oxide addition product etc.

As carboxylic acid or its acid anhydrides, can list the dibasic acid such as phthalic acid, m-phthalic acid, terephthalic acid (TPA), hexane diacid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid or its acid anhydrides etc.

Epoxy (methyl) acrylate is to make (methyl) acrylic acid and epoxy resin carry out the compound that addition reaction forms.As epoxy resin, can list aromatic epoxy resin and aliphatic epoxy resin etc.

As aromatic epoxy resin, can specifically list resorcinolformaldehyde resin; Two or polyglycidyl ether of bisphenol-A, Bisphenol F, bisphenol S, bisphenol fluorene or its alkylene oxide addition product; The phenol aldehyde type epoxy resins such as phenol phenol aldehyde type epoxy resin and cresols phenol aldehyde type epoxy resin; Glycidyl phthalimide; O-phthalic acid diglycidyl ester etc.

Except them, also can list at the document progress of the epoxy resin-nearest "-" (clear rolling hall, nineteen ninety publishes) 2 chapters, increase such compound of record in 4～6 pages, 9～16 pages of number of the edition epoxy resin (meeting of macromolecule publication, clear and publication in 48 years) at document " Process Technology of Polymer " fascicle the 9, the 22nd volume.

As aliphatic epoxy resin, can specifically list the diglycidyl ether of the aklylene glycols such as ethylene glycol, propylene glycol, BDO and 1,6-hexanediol; The diglycidyl ether of the poly alkylene glycol such as the diglycidyl ether of polyglycol and polypropylene glycol; The diglycidyl ether of neopentyl glycol, dibromoneopentyl glycol and alkylene oxide addition product thereof; The polyglycidyl ether of the polyvalent alcohols such as two, three or four glycidol ethers of two or triglycidyl ether of trimethylolethane, trimethylolpropane, glycerine and alkylene oxide addition product thereof and pentaerythrite and alkylene oxide addition product thereof; Two or polyglycidyl ether of hydrogenated bisphenol A and alkylene oxide addition product thereof; Tetrahydrophthalic acid diglycidyl ether; P-dihydroxy-benzene diglycidyl ether etc.

Except them, can list the compound of recording in 3～6 pages of above-mentioned document " Process Technology of Polymer " fascicle epoxy resin.Except these aromatic epoxy resins and aliphatic epoxy resin, also can list the epoxy compound in skeleton with triazine core, such as TEPIC(daily output chemistry (strain)), long rapids the changing into of DENACOL EX-310((strain)) etc., maybe can list such compound of recording etc. in 289～296 pages of above-mentioned document " Process Technology of Polymer " fascicle epoxy resin.

In above-mentioned, as the alkylene oxide of alkylene oxide addition product, be preferably oxirane and epoxypropane etc.

As polyethers (methyl) acrylate oligomer, there is poly alkylene glycol (methyl) diacrylate, can list polyglycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate and polytetramethylene glycol two (methyl) acrylate etc.

As carbamate (methyl) acrylate oligomer, can enumerate reaction product that send as an envoy to polyvalent alcohol and organic multiple isocyanate reaction product further form with (methyl) acrylate reactions of hydroxyl etc.As polyvalent alcohol, there are low molecular weight polyols, polyglycol and polyester polyol etc. herein.As low molecular weight polyols, can list ethylene glycol, propylene glycol, cyclohexanedimethanol and 3-methyl isophthalic acid, 5-pentanediol etc., as polyether glycol, can list polyglycol and polypropylene glycol etc., as polyester polyol, can list these low molecular weight polyols or/and the reaction product of the sour compositions such as the dibasic acid such as polyether glycol and hexane diacid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid (TPA) or its acid anhydrides.As organic multiple isocyanate, can list toluene diisocyanate, 4,4 '-methyl diphenylene diisocyanate, HMDI, hexamethylene diisocyanate and isophorone diisocyanate etc.As (methyl) acrylate of hydroxyl, can list (methyl) acrylic acid-2-hydroxyl ethyl ester and (methyl) 2-hydroxypropyl acrylate etc. (methyl) acrylic acid hydroxy alkyl ester etc.These carbamates (methyl) acrylate oligomer is as long as manufacture according in the past known synthetic method.Can enumerate as under existing at addition catalysts such as dibutyltin dilaurates, by used organic isocyanate with polyol component adds thermal agitation and make it carry out addition reaction, add again (methyl) acrylic acid hydroxy alkyl ester, add thermal agitation and make its method of carrying out addition reaction etc.

As the molecular weight of carbamate (methyl) acrylate oligomer, from the viewpoint of making the excellent in te pins of durability of cured film of composition of gained, be preferably 500～10 in number-average molecular weight, 000, more preferably 1,000～10,000.

The molecular weight distribution (the matter average molecular weight (Mw) of measuring by gel permeation chromatography (GPC) and the ratio of number-average molecular weight (Mn)) of above-mentioned (P) organic polymer is though be not particularly limited, but be preferably less than 1.8, more preferably below 1.7, more preferably below 1.6, be particularly preferably below 1.5, especially be preferably below 1.4, most preferably be below 1.3.

The lower limit of the number-average molecular weight of above-mentioned (P) organic polymer is preferably 500, and more preferably 3,000, the upper limit is preferably 100,000, and more preferably 40,000.If molecular weight less than 500, has the tendency that is difficult to show the original characteristic of polymkeric substance, if exceed 100,000, there is the tendency of processing variable difficulty.

By coordinating in the present invention (P) composition, can show sufficient bounding force, during for bonding agent etc., can be temporarily fixing by adhesives in bonding operation.In addition, (P) composition can improve the cohesiveness of solidfied material, can improve thermotolerance.

Composition (P) though mixing ratio be not particularly limited, be preferably 0.1～100 mass parts with respect to composition (A) 100 mass parts, more preferably 1～50 mass parts.If exceed 100 mass parts, uprise the tendency that the workability such as coating reduce in viscosity.Above-mentioned (P) organic polymer can be used alone and also can be used in combination.

There is (methyl) acrylate monomer of alkyl as above-mentioned (D), though can use known (methyl) acrylate based compound with alkyl, but be preferably the material without polar group, for example, be preferably (methyl) acrylate, ester ring type (methyl) acrylate monomer of the branched-chain alkyl alcohol of (methyl) alkyl acrylate, the carbon number 13～20 of the alkyl with carbon number 1～12.

As (methyl) alkyl acrylate of the above-mentioned alkyl with carbon number 1～12, can enumerate as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) acrylic acid isopentyl ester, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, (methyl) acrylic acid ester in the positive last of the ten Heavenly stems, (methyl) isodecyl acrylate, (methyl) dodecylacrylate, (methyl) lauryl acrylate etc.They can be used alone, also can two or more and use.

As (methyl) acrylate of the branched-chain alkyl alcohol of above-mentioned carbon number 13～20, can enumerate as acrylate and the methacrylate of different tetradecanol (another name: different myristyl alcohol), different pentadecanol, isohexadecane alcohol, different heptadecanol, isooctadecane alcohol (another name: isooctadecanol), norphytane alcohol, eicosanol etc.Above-mentioned chain acrylate and methacrylate can be distinguished and use separately or two or more appropriately combined use.

As above-mentioned ester ring type (methyl) acrylate monomer, be preferably (methyl) acrylate monomer of the alkyl with ring-type, for example, can exemplify known material in Japanese kokai publication sho 61-136529 communique, Japanese kokai publication hei 2-588529 communique etc., can specifically list: (methyl) cyclohexyl acrylate, (methyl) acrylic acid norborneol ester, (methyl) acrylic acid dicyclo pentyl ester, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) isobornyl acrylate etc.

By coordinating in the present invention (D) composition, can improve flexibility.

Composition (D) though mixing ratio be not particularly limited, be preferably 1～500 mass parts with respect to composition (A) 100 mass parts, more preferably 10～200 mass parts.Composition (D) can be used alone also can two or more and use.

What have polar group as above-mentioned (E) is the monomer of base containing (methyl) acryloyl, can use that to have (methyl) acryloyl shown in polar group and above-mentioned general formula (1) be the known compound of base, can enumerate as: carboxylic (methyl) acryloyls such as (methyl) acrylic acid, itaconic acid, (methyl) acrylic acid carboxyl ethyl ester, (methyl) acrylic acid carboxyl propyl ester are monomer; (methyl) acryloyl that (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid-4-hydroxy butyl ester, caprolactone modification (methyl) acrylate, polyglycol (methyl) acrylate, polypropylene glycol (methyl) acrylate etc. have hydroxyl is monomer; Nitrogenous (methyl) acryloyls such as (methyl) acrylic acid dimethylamino methyl esters, (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid dimethylamino propyl ester, (methyl) acrylic acid diethylamino ethyl ester are monomer etc., be preferably carboxylic (methyl) acrylic monomer and nitrogenous (methyl) acrylic monomer, more preferably carboxylic (methyl) acrylic monomer.They can be used alone, also can two or more and use.

By coordinating in the present invention (E) composition, can make cohesiveness improve, cementability and heat-resisting creep properties are improved.

Composition (E) though mixing ratio be not particularly limited, with respect to composition (A) 100 mass parts, be preferably 0.1～30 mass parts, more preferably 0.5～20 mass parts.Composition (E) can be used alone also can two or more and use.

In the present invention, can and use and there is the ethene base system monomer that (methyl) acryloyl shown in polar group and above-mentioned general formula (1) is the vinyl beyond base.As the ethene base system monomer of this polar functionalities, can enumerate as crotonic acid, maleic acid (acid anhydride), fumaric acid (acid anhydride), (methyl) vinyl cyanide, NVP, N-caprolactam, N-vinyl lauric lactam, (methyl) acryloyl morpholine, (methyl) acrylamide, dimethyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, dimethylformamide propyl group (methyl) acrylamide etc.

As above-mentioned (G) 1 or 2 functionalities what have phosphate is the monomer of base containing (methyl) acryloyl, can enumerate as: single (2-methacryloxyethyl) phosphate ester acid, i.e. CH ₂=C(CH ₃) COO(CH ₂) ₂oPO(OH) ₂, single (3-methacryloxypropyl) phosphate ester acid is CH ₂=C(CH ₃) COO(CH ₂) ₃oPO(OH) ₂, single (2-acrylyl oxy-ethyl) phosphate ester acid is CH ₂=CHCOO(CH ₂) ₂oPO(OH) ₂, single (3-acryloyl-oxy propyl group) phosphate ester acid is CH ₂=CHCOO(CH ₂) ₃oPO(OH) ₂deng 2 functionalities have phosphate containing (methyl) acryloyl be the monomer of base; Two (2-methacryloxyethyl) phosphate ester acid i.e. [CH ₂=C(CH ₃) COO(CH ₂) ₂o] ₂pO(OH), the i.e. [CH of two (3-methacryloxypropyl) phosphate ester acid ₂=C(CH ₃) COO(CH ₂) ₃o] ₂pO(OH), the i.e. [CH of two (2-acrylyl oxy-ethyl) phosphate ester acid ₂=CHCOO(CH ₂) ₂o] ₂pO(OH), the i.e. [CH of two (3-acryloyl-oxy propyl group) phosphate ester acid ₂=CHCOO(CH ₂) ₃o] ₂etc. PO(OH) 1 functionality what have phosphate is the monomer of base containing (methyl) acryloyl, or their mix monomer.While using mix monomer, can suitably change the mixing ratio of each monomer.

Among them, consider from the viewpoint of adaptation, water tolerance, be preferably 1 functionality what have phosphate is the monomer of base containing (methyl) acryloyl, more preferably two (2-methacryloxyethyl) phosphate ester acid.

In addition, the monomer that is base containing (methyl) acryloyl with phosphate that the type that has a following structure also can be used as 1 or 2 functionalities uses.

CH ₂=C（CH ₃）COO（CH ₂） _lOCO-R-CO-OPO（OH）R’

(in formula, R is for can have substituent (CH ₂) _kor C ₆h ₄, R ' is hydroxyl or CH ₂=C(CH ₃) COO(CH ₂) _noCO-R-CO-O-base, l, k and n are respectively 1～6 integer independently.）

It is above-mentioned that what have phosphate is that the monomer of base is commercially available with following trade name containing (methyl) acryloyl.Can enumerate as Light ester P-1M more than Light ester P-2M(, chemical company of common prosperity society system), more than Phosmer M(, Uni-Chemical company system).

In Photocurable composition of the present invention, by coordinating (G) composition, give play to the very large effect that the curability can make cementability, heat-resisting creep properties and black time improves.

Composition (G) though mixing ratio be not particularly limited, with respect to composition (A) 100 mass parts, be preferably 0.01～20 mass parts, more preferably 0.1～10 mass parts.Sometimes can not obtain fully initial cementability if be less than 0.01 mass parts, curing rate is slack-off sometimes.In addition, if more than 20 mass parts, storage stability reduces sometimes, the tendency that has water tolerance to reduce.Composition (G) can be used alone also can two or more and use.

Be not particularly limited as the above-mentioned multifunctional monomer (H) that is base containing (methyl) acryloyl, can enumerate as ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1, 6-hexanediol two (methyl) acrylate, 2 functionalities (methyl) acrylic monomers such as trimethylolpropane two (methyl) acrylate, 3 functionalities (methyl) acrylic monomers such as trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, 4 officials such as pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate can be above (methyl) acrylic monomer etc.According to initial bonding force and stable on heating balance, be preferably 2 functionalities (methyl) acrylic monomer, 3 functionalities (methyl) acrylic monomer, more preferably 2 functionalities (methyl) acrylic monomer.

In Photocurable composition of the present invention, by coordinating (H) composition, can make thermotolerance improve.

Composition (H) though mixing ratio be not particularly limited, with respect to composition (A) 100 mass parts, be preferably 0.01～20 mass parts, more preferably 0.02～10 mass parts.If be less than 0.01 mass parts, heat-resisting creep properties reduces sometimes, if more than 20 mass parts, sometimes can not obtain fully initial cementability.Composition (H) can be used alone also can two or more and use.

In Photocurable composition of the present invention, use (C) curing accelerator.(methyl) acrylic ester polymer that (A) using in the present invention on average has more than 0.8 bridging property silicyl in 1 molecule utilizes water, airborne hygroscopic water to form siloxane bond in the presence of or not the existence of known various curing accelerator (also referred to as curing catalysts, condensation catalyst) in the past or at it, is cross-linked, curing.

In Photocurable composition of the present invention, as above-mentioned (C) curing accelerator, can be widely used the known curing accelerator of the cross-linking reaction of promotion (A) (methyl) acrylic ester polymer, be not particularly limited, can enumerate as photoacid generator, Photobase generator, silicon alcohol condensation catalyst etc., particularly from working as curing accelerator irradiation, after can being coated with on the base materials such as unit, guarantee the viewpoint consideration of running time, be preferably photoacid generator.In addition, because the sour generation efficiency after light irradiation is good, pretend and be preferably sulfosalt and salt compounded of iodine, more preferably sulfosalt for composition (C).

As the sulphion in above-mentioned sulfosalt, can enumerate as triphenyl sulphur, three p-methylphenyl sulphur, tri-o-tolyl sulphur, three (4-methoxyphenyl) sulphur, 1-naphthyl diphenyl sulphur, 2-naphthyl diphenyl sulphur, three (4-fluorophenyl) sulphur, three-1-naphthyl sulphur, three-2-naphthyl sulphur, three (4-hydroxy phenyl) sulphur, 4-(thiophenyl) phenyl diphenyl sulphur, 4-(p-methylphenyl sulfenyl) phenyl di-p-tolyl sulphur, 4-(4-methoxybenzene sulfenyl) two (4-methoxyphenyl) sulphur of phenyl, 4-(thiophenyl) two (4-fluorophenyl) sulphur of phenyl, 4-(thiophenyl) two (4-methoxyphenyl) sulphur of phenyl, 4-(thiophenyl) phenyl di-p-tolyl sulphur, two [4-(diphenyl sulfonium base) phenyl] thioether, two (4-{ pair [4-(2-hydroxyl-oxethyl) phenyl] sulfonium base } phenyl) thioether, two two (4-fluorophenyl) the sulfonium bases of 4-[] and phenyl } thioether, two two (4-aminomethyl phenyl) the sulfonium bases of 4-[] and phenyl } thioether, two two (4-methoxyphenyl) the sulfonium bases of 4-[] and phenyl } thioether, 4-(4-benzoyl-2-chlorobenzene sulfenyl) two (4-fluorophenyl) sulphur of phenyl, 4-(4-benzoyl-2-chlorobenzene sulfenyl) phenyl diphenyl sulphur, 4-(4-benzoyl thiophenyl) two (4-fluorophenyl) sulphur of phenyl, 4-(4-benzoyl thiophenyl) phenyl diphenyl sulphur, 7-isopropyl-9-oxa--10-sulphur-9,10-anthracene dihydride-2-base di-p-tolyl sulphur, 7-isopropyl-9-oxa--10-sulfo--9,10-anthracene dihydride-2-base diphenyl sulphur, 2-[(di-p-tolyl) sulfonium base] thioxanthones, 2-[(diphenyl) sulfonium base] thioxanthones, 4-[4-(4-tert-butyl benzene formoxyl) thiophenyl] phenyl di-p-tolyl sulphur, 4-[4-(4-tert-butyl benzene formoxyl) thiophenyl] phenyl diphenyl sulphur, 4-[4-(benzoyl thiophenyl)] phenyl di-p-tolyl sulphur, 4-[4-(benzoyl thiophenyl)] phenyl diphenyl sulphur, 5-(4-methoxyphenyl) thianthrene (Thianthrenium), 5-phenyl thianthrene, 5-tolyl thianthrene, 5-(4-ethoxyl phenenyl) thianthrene, 5-(2,4,6-trimethylphenyl) the triaryl sulphur such as thianthrene, the diaryl sulphur such as diphenyl phenacyl sulphur, diphenyl 4-nitrobenzene formyl methyl sulphur, diphenyl dibenzylsulfide, diphenyl methyl sulphur, phenyl methyl dibenzylsulfide, 4-hydroxy phenyl methyl-benzyl sulphur, 4-methoxyphenyl methyl-benzyl sulphur, 4-acetyl carbonyl oxygen base phenyl methyl dibenzylsulfide, 2-naphthyl methyl dibenzylsulfide, 2-naphthyl methyl (1-ethoxy carbonyl) ethyl sulphur, phenyl methyl phenacyl sulphur, 4-hydroxy phenyl toluyl methyl sulphur, 4-methoxyphenyl toluyl methyl sulphur, 4-acetyl carbonyl oxygen base phenyl methyl phenacyl sulphur, 2-naphthyl methyl phenacyl sulphur, 2-naphthyl octadecyl phenacyl sulphur, single aryl sulphur such as 9-anthryl toluyl methyl sulphur, the trialkyl sulphur such as dimethyl phenacyl sulphur, phenacyl thiophane, dimethyl benzyl sulphur, benzyl tetrahydro thiophene, octadecyl methyl phenacyl sulphur etc.

As the iodide ion in above-mentioned salt compounded of iodine, can enumerate as diphenyl iodine, di-p-tolyl iodine, two (4-dodecylphenyl) iodine, two (4-methoxyphenyl) iodine, (4-octyloxyphenyl) phenyl-iodide, two (4-oxygen in last of the ten Heavenly stems base phenyl) iodine, 4-(2-hydroxyl tetradecyloxyaniline) phenyl iodine, 4-isopropyl phenyl (p-methylphenyl) iodine, isobutyl phenenyl (p-methylphenyl) iodine etc.

Among them, particularly preferred material can list triphenyl sulphur, three p-methylphenyl sulphur, 4-(thiophenyl) phenyl diphenyl sulphur, two [4-(diphenyl sulfonium base) phenyl] thioether, two (4-{ pair [4-(2-hydroxyl-oxethyl) phenyl] sulfonium base } phenyl) thioether, two two (4-fluorophenyl) the sulfonium bases of 4-[] and phenyl } thioether, 4-(4-benzoyl-2-chlorobenzene sulfenyl) two (4-fluorophenyl) sulphur of phenyl, 4-(4-benzoyl thiophenyl) phenyl diphenyl sulphur, 7-isopropyl-9-oxa--10-sulfo--9,10-anthracene dihydride-2-base di-p-tolyl sulphur, 7-isopropyl-9-oxa--10-sulfo--9,10-anthracene dihydride-2-base diphenyl sulphur, 2-[(di-p-tolyl) sulfonium base] thioxanthones, 2-[(diphenyl) sulfonium base] thioxanthones, 4-[4-(4-tert-butyl benzene formoxyl) thiophenyl] phenyl di-p-tolyl sulphur, 4-[4-(benzoyl thiophenyl)] phenyl diphenyl sulphur, 5-(4-methoxyphenyl) thianthrene, 5-phenyl thianthrene, diphenyl phenacyl sulphur, 4-hydroxy phenyl methyl-benzyl sulphur, 2-naphthyl methyl (1-ethoxy carbonyl) ethyl sulphur, sulphion and the diphenyl iodine of 4-hydroxy phenyl toluyl methyl sulphur and octadecyl methyl phenacyl sulphur etc., di-p-tolyl iodine, two (4-dodecylphenyl) iodine, two (4-methoxyphenyl) iodine, (4-octyloxyphenyl) phenyl-iodide, two (4-oxygen in last of the ten Heavenly stems base) phenyl-iodide, 4-(2-hydroxyl tetradecyloxyaniline) phenyl iodine, the iodide ion of 4-isopropyl phenyl (p-methylphenyl) iodine and 4-isobutyl phenenyl (p-methylphenyl) iodine etc.In addition, can use the kation of recording in WO2011/016425.

Though the counter anion as above-mentioned photoacid generator is not particularly limited, preferably has and be selected from (R ¹¹sO ₂) ₂n ^-, (R ¹¹sO ₂) ₃c ^-, R ¹¹sO ₃ ^-and PF ₆ ^-in a kind of above negative ion (R herein, ¹¹represent alkyl, the perfluoroalkyl of carbon number 1～20 or the aryl of carbon number 6～20 of carbon number 1～20, alkyl and perfluoroalkyl can be any in straight chain, a chain or ring-type, and aryl can be unsubstituted, also can have substituting group.) as counter anion, from the viewpoint of more preferably (R of cementability ¹¹sO ₂) ₂n ^-, (R ¹¹sO ₂) ₃c ^-, R ¹¹sO ₃ ^-.

As (R ¹¹sO ₂) ₂n ^-represented negative ion, can list (CF ₃sO ₂) ₂n ^-, (C ₂f ₅sO ₂) ₂n ^-, (C ₃f ₇sO ₂) ₂n ^-or (C ₄f ₉sO ₂) ₂n ^-deng.

As (R ¹¹sO ₂) ₃c ^-represented negative ion, can list (CF ₃sO ₂) ₃c ^-, (C ₂f ₅sO ₂) ₃c ^-, (C ₃f ₇sO ₂) ₃c ^-or (C ₄f ₉sO ₂) ₃c ^-deng.

As R ¹¹sO ₃ ^-represented negative ion, can list trifluoromethayl sulfonic acid negative ion, pentafluoroethane sulfonic acid anion, heptafluoro-propane sulfonic acid anion, nine fluorine butane sulfonic acid anions, pentafluorophenyl group sulfonic acid anion, p-toluenesulfonic acid negative ion, benzene sulfonic acid negative ion, camphorsulfonic acid negative ion, Loprazolam negative ion, ethane sulfonic acid negative ion, propane sulfonic acid negative ion and butane sulfonic acid anion etc.Among them, preferably trifluoromethayl sulfonic acid negative ion, nine fluorine butane sulfonic acid anions, benzene sulfonic acid negative ion or p-toluenesulfonic acid negative ion.

Among these negative ion, more preferably trifluoromethayl sulfonic acid negative ion, nine fluorine butane sulfonic acid anions, benzene sulfonic acid negative ion or p-toluenesulfonic acid negative ion, (CF ₃sO ₂) ₃c ^-, (CF ₃sO ₂) ₂n ^-.

Useful nonionic is that photoacid generator replaces above-mentioned sulfosalt and salt compounded of iodine, but sour generation efficiency when being irradiated by light is good, therefore preferably sulfosalt and salt compounded of iodine.

Be photoacid generator as this nonionic, can be widely used known nonionic is photoacid generator, though be not particularly limited, but can enumerate as sulphones, sulfonate compound, sulfone imide compound, disulfonyl base two azomethane compounds, disulfonyl methylmethane compound, oxime sulfonates compound, hydrazine sulfonate compound, triaizine compounds, nitrobenzyl (ニ ト ロ ベ Application ジ Le) compound, organohalogen compounds class, two sulfones etc., be preferably and be selected from sulphones, sulfone imide compound, in two azomethane compounds and oxime sulfonates compound more than a kind.

As above-mentioned sulphones, can enumerate as β-one sulfone, 'Beta '-sulfonyl sulfone or their α-bis-azo-compound etc.

In addition, as above-mentioned sulfonate compound, can enumerate as alkyl sulfonic ester, alkylhalide group sulphonic acid ester, aromatic yl sulphonate, imino group sulphonic acid ester etc.

In addition, as above-mentioned acid imide sulfonate compound, can be listed below and state the represented compound of general formula (3).

[changing 1]

(in general formula (3), R ¹²represent the organic group of 1 valency, R ¹³represent the organic group of divalent.〕

In addition, as above-mentioned disulfonyl base two azomethanes, can be listed below and state the represented compound of general formula (4).

[changing 2]

(in general formula (4), each R ¹⁴the halogen that represents independently of each other 1 valency of aliphatic alkyl, naphthenic base, straight chain shape or a chain of 1 valency of straight chain shape or a chain replaces aliphatic alkyl, halogen substituted cycloalkyl, aryl, halogenated aryl etc.〕

In addition, as above-mentioned disulfonyl methylmethane compound, can be listed below and state the represented compound of general formula (5).

[changing 3]

(in general formula (5), each R ¹⁵represent independently of each other straight chain shape or chain 1 valency aliphatic alkyl, naphthenic base, aryl, aralkyl or there is the organic group of heteroatomic 1 valency, V and W represent independently of each other aryl, hydrogen atom, straight chain shape or a chain 1 valency aliphatic alkyl or there are other organic groups of heteroatomic 1 valency, and at least one in V and W is aryl, or V and W interconnect and form and have the monocycle of at least 1 unsaturated link or encircle more, or V and W interconnect and form (i) represented group of following formula.〕

[changing 4]

(formula (i) in, V ' and W ' are separate, and can be the same or different between multiple V ' and between W ', it represents alkyl, naphthenic base, the aryl or aralkyl of hydrogen atom, halogen atom, straight chain shape or a chain, or interconnect and form carbocyclic ring structure, the integer that x is 2～10 from V ' and the W ' of identical or different carbon atom bondings.〕

In addition, as above-mentioned oxime sulfonates compound, can be listed below and state general formula (6-1) or the represented compound of general formula (6-2).

[changing 5]

[changing 6]

(in general formula (6-1) and general formula (6-2), R ¹⁶and R ¹⁷represent independently of each other the organic group of 1 valency, the R of two in general formula (6-2) ¹⁶between and the R of two ¹⁷between can distinguish identical also can be different.〕

As the concrete example of above-mentioned oxime sulfonates compound, can list α-(tolysulfonyl oxygen base imino group) phenylacetonitrile, α-(phenylsulfonyloxy imino group)-2, 4-dichlorophenyl acetonitrile, α-(phenylsulfonyloxy imino group)-2, 6-dichlorophenyl acetonitrile, α-(2-chlorobenzene sulfonyloxy imino group)-4-methoxyphenyl acetonitrile, α-(ethyl sulfonyloxy imino group)-1-cyclopentenyl acetonitrile, α-(sulfonyloxy methyl oxygen base imino group)-1-phenylacetonitrile, α-(sulfonyloxy methyl oxygen base imino group)-1-(p-methylphenyl) acetonitrile, α-(sulfonyloxy methyl oxygen base imino group)-1-(p-methoxyphenyl) acetonitrile, (2-(sulfonyl propyl oxygen base imino group)-2, 3-dihydroxy thiophene-3-subunit) (o-tolyl) acetonitrile and following chemical formula (7-1)～(7-8) represented material.

[changing 7]

[changing 8]

In addition, as above-mentioned hydrazine sulfonate compound, can enumerate as general formula (8-1) or the represented compound of general formula (8-2).

[changing 9]

(in general formula (8-1) and general formula (8-2), R ¹⁸represent the organic group of 1 valency, the R of two in general formula (6-2) ¹⁸can be mutually identical also can be different.〕

Composition (C) though mixing ratio be not particularly limited, with respect to composition (A) 100 mass parts, be preferably 0.01～20 mass parts, more preferably 0.1～10 mass parts.If composition (C) is less than 0.01 mass parts, there is the slack-off situation of curing rate.

As above-mentioned silicon alcohol condensation catalyst, for example, can exemplify the titanate esters such as butyl titanate, metatitanic acid orthocarbonate, tetraisopropyl titanate, four titanium acetylacetones; The 4 valency tin compounds such as the reaction product of dibutyl tin laurate, maleic acid dibutyl tin, dibutyltin diacetate, dibutyl diacetyl acetone tin, Dibutyltin oxide, two dioctyltin laurate, dioctyl tin maleate, oxalic acid dioctyl tin, two neodecanoic acid dioctyl tins (two koch's acid dioctyl tins), dioctyl tin oxide, Dibutyltin oxide and phthalic ester; The organo-tin compound classes such as divalent tin compound such as tin octoate, naphthenic acid tin, stearic acid tin, two neodecanoic acid tin (koch's acid tin); The organo-aluminum compound classes such as praseodynium aluminium, aluminium triethyl acetoacetic ester, diisopropoxy aluminium ethyl acetoacetic ester; The reaction product of the bismuth salt such as three (2 ethyl hexanoic acid) bismuth, three (neopentanoic acid) bismuth and organic carboxyl acid or organic amine etc.; The chelate classes such as four diacetone zirconiums, four titanium acetylacetones; The organo-lead compounds such as lead octoate; The organoiron compounds such as iron naphthenate; Organic vanadium compound; Butylamine, octylame, lauryl amine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, two sub-second triamines, Sanya second tetramine, oleyl amine, cyclohexylamine, benzylamine, diethylaminopropylamine, sub-dimethylphenylene diamine, Sanya ethylenediamine, guanidine, diphenylguanidine, 2,4,6-tri-(dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecylene-7(DBU) etc. the salt of amine compound or they and carboxylic acid etc.; The low-molecular-weight polyamide resin being obtained by excessive polyamines and polyprotonic acid; Excessive polyamines and the reaction product of epoxy compound etc.But according to the addition of uncle or secondary amine compound, the storage stability of the Photocurable composition of gained reduces sometimes.

Composition (C) can be used alone also can two or more and use.In addition, when composition (C) is photoacid generator, can with known other photoacid generators using in the past such as other salt compounds.Above-mentioned photoacid generator can dilute, coordinate in the organic solvents such as propylene carbonate in addition.

As above-mentioned (F) optical free radical initiating agent, can be widely used known optical free radical initiating agent, be not particularly limited, can enumerate as benzoin ethers such as benzoin ethyl ether, benzoin butyl ether and benzoin iso-propylethers, 4,4 '-bis-dimethylamino benzophenone and 4,4 '-benzophenones such as bis-diethylamino benzophenone, acetophenone, 2, 2-dimethoxy-2-phenyl acetophenone, 2, 2-diethoxy-2-phenyl acetophenone, 1, 1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-[4-(2-hydroxyl-oxethyl)-phenyl-]-2-hydroxy-2-methyl-1-propane-1-ketone, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propiono)-benzyl] phenyl }-2-methyl-propane-1-ketone, 2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base-phenyl)-butane-1-ketone and N, the acetophenones such as N-dimethylamino benzoylformaldoxime, the thioxanthene ketones such as 2,4-diethyl thioxanthone, CTX and ITX, the ketal classes such as benzil dimethyl ketal, acetophenone dimethyl ketal, the phosphinoxidess such as TMDPO, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, ethyl ESCAROL 507 ester, (2-dimethylamino) ethylamino benzonitrile acid esters, two-4, the amine synergists such as 4 '-dimethylamino benzophenone etc.

Among them, preferred 2-methyl isophthalic acid aspect the curability of deep-(4-(methyl mercapto) phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1 and 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base-phenyl)-alpha-aminoacetophenone the classes such as butane-1-ketone; The acylphosphine oxide classes such as TMDPO, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide; And amine synergist etc. for example, has the optical free radical initiating agent of light absorption, more preferably acylphosphine oxide class and amine synergist long wavelength's (, wavelength 300nm).

In addition, produce because the benzil ketals classes such as benzil dimethyl ketal promote acid, work as sensitizer, so preferably.

In addition; 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-[4-(2-hydroxyl-oxethyl)-phenyl-]-2-hydroxy-2-methyl-1-propane-1-ketone, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propiono)-benzyl] phenyl-alpha-hydroxyacetophenone classes such as 2-methyl-propane-1-ketone can make surface cure improve, thereby preferably.

Composition (F) though mixing ratio be not particularly limited, with respect to composition (B) 100 mass parts, be preferably 0.01～20 mass parts, more preferably 0.1～10 mass parts.Composition (F) can be used alone also can two or more and use.

By coordinate (I) resin extender in Photocurable composition of the present invention, can strengthen solidfied material, heat-resisting creep properties is improved.Above-mentioned resin extender (I) is the granular filler that comprises organic resin etc., can use the known organic particulates such as polyethyl acrylate, polyurethane, tygon, polypropylene.

Be for example filler as Lauxite, can list " PERGOPAK series " etc. that ALBEMARLE company manufactures.Be filler as melamine resin in addition, can list " EPOSTAR M30 " etc. that Nippon Shokubai Co., Ltd manufactures.Be filler as carbamate resins in addition, can list crosslinked carbamate bead such as " Art-Pearl C-200, C-300, C-400, C-800 " that Negami Chemical Ind Co., Ltd. manufactures etc.In addition, be filler as benzene for guanamine resin, can list " EPOSTAR M05, MS " etc. that Nippon Shokubai Co., Ltd manufactures.Be filler as phenolics, can list " PR-RES-5 ", " the Shonol PMB-1010 " that clear and macromolecule company manufactures etc. that Sumitomo Bakelite company manufactures.Be filler as acrylic resin, can list " Techpolymer MBX series " etc. that Sekisui Plastics Co., Ltd. manufactures.In addition, be filler as styrene resin, can list " Techpolymer SBX series " etc. that Sekisui Plastics Co., Ltd. manufactures.

As above-mentioned resin extender (I), being preferably carbamate resins aspect good to the compatibility of composition (A), (B) is that filler, acrylic resin are filler, and more preferably carbamate resins is filler.

The mean grain size of resin extender (I) is 1～150 μ m, is preferably 5～30 μ m.In the present invention, above-mentioned mean grain size is by laser refraction scattering method.If mean grain size is less than 1 μ m, sometimes becomes and in the system of composition, be difficult to disperse.In addition, there is the nozzle of spreader to become susceptible to plugging tendency if be greater than 150 μ m.

The Tg of above-mentioned (I) resin extender is preferably 20 DEG C～-60 DEG C, more preferably 0 DEG C～-50 DEG C.It should be noted that, Tg measures by differential scanning calorimetry (DSC method).If, lower than-60 DEG C, becoming sometimes, Tg in the system of composition, is difficult to disperse.In addition, if higher than 20 DEG C of heat-resisting creep properties reductions sometimes.

When Photocurable composition of the present invention is used for requiring the purposes of light-proofness, above-mentioned (I) resin extender preferably comprises the resin extender of black.In the past, if add deep curability variation of light-proofness material in Photocurable composition, there is thick film to solidify the problem that becomes difficult, when seeking to give light-proofness, can obtain the material of good deep curability.By use the resin extender of black of mean grain size 1～150 μ m in Photocurable composition of the present invention, even if also can obtain good deep curability in the case of using the LED lamp etc. of single wavelength, can reach excellent light-proofness and deep curability.Further, because having improved deep curability, therefore also can make heat-resisting creep properties improve.

Composition (I) though mixing ratio be not particularly limited, with respect to composition (A) and 100 mass parts of total (B), be preferably 0.5～200 mass parts, more preferably 1～50 mass parts.If be less than the heat-resisting creep properties reduction sometimes of 0.5 mass parts, if sometimes can not obtain fully initial cementability more than 200 mass parts.Composition (I) can be used alone also can two or more and use.

Photocurable composition of the present invention preferably also contains (J) moisture absorber.

As above-mentioned moisture absorber, silane coupling agent described later, silicate are preferred.As above-mentioned silicate, be not particularly limited, can enumerate as tetraalkoxysilane or its partial hydrolysis condensation product, can more specifically list tetraalkoxysilane (tetraalkyl silicate) and their the partial hydrolysis condensation products such as tetramethoxy-silicane, tetraethoxysilane, ethoxy trimethoxy silane, dimethoxy diethoxy silane, methoxyl triethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, tetraisobutoxy-silicane alkane, four tert-butoxy silane.

As the silane coupling agent as (J) moisture absorber, as long as the material working as moisture absorber is just not particularly limited, but be preferably the silanes containing ethylenically unsaturated group that contains vinyl beyond vinyltrimethoxy silane, vinyltriethoxysilane etc. (methyl) acryloyl group; The alkyl silane classes such as hexyl trimethoxy silane, hexyl triethoxysilane, decyl trimethoxy silane; Containing the silanes of phenyl.

Composition (J) though mixing ratio be not particularly limited, with respect to composition (A), (B) and 100 mass parts of total (I), be preferably 0.1～50 mass parts, more preferably 1～50 mass parts.If be less than the tendency that 0.1 mass parts has curability (UV, moisture-curable both) to reduce.In addition, if more than 50 mass parts, the tendency that has storage stability to reduce.Composition (J) can be used alone also can two or more and use.

When Photocurable composition of the present invention is used for requiring the purposes of light-proofness, can coordinate above-mentioned black resin filler (K) light-proofness material in addition.Should (K) light-proofness material be the material of Photocurable resin composition being given to light-proofness, be preferably black pigment.If composition (K) is too much, because there being the risk of the unfavorable condition such as the reduction of solidfied material physical property or photo-curable reduction that composition occurs, therefore preferably give the light-proofness material of light-proofness with a small amount of interpolation.As composition (K), can list inorganic or organic pigment.As inorganic pigment, can list carbon dust, ivory black, Mars black (Mars Black), peach black (Peach Black), dim, cupric, iron, chromium, manganese, cobalt etc. inorganic be black, titanium is black etc.Be preferably carbon dust, more preferably carbon black, acetylene black, Ketjen black, carbon nano-tube, native graphite powder, Delanium powder etc., the viewpoint of giving light-proofness to the Photocurable composition solidifying from the interpolation with a small amount of is considered, is particularly preferably carbon black, acetylene black, Ketjen black.As organic pigment, can list nigrosine, perylene black, You Xuan Wei perylene is black.As commercially available goods, can list the black pigment (goods name: NBD-0744) of Nikko bics Co., Ltd. manufacture etc.

Composition (K) though mixing ratio be not particularly limited, with respect to composition (A), (B) and 100 mass parts of total (I), be preferably 0.001～20 mass parts, more preferably 0.01～10 mass parts.If be less than 0.001 mass parts, sometimes can not obtain sufficient light-proofness, if more than 20 mass parts, thick film curability reduces.Composition (K) can be used alone also can two or more and use.

Other adjuvants of < >

In Photocurable composition of the present invention, with the object that is adjusted into of each physical property of Photocurable composition or its solidfied material, can add as required various adjuvants.As the example of such additive, can enumerate as: packing material, antioxidant, plastifier, reactive diluent, light stabilizer, tackifier, solvent, photosensitizer, fire retardant, antiaging agent, free radical inhibitors, metal passivator, antiozonant, phosphorus are peroxide decomposer, lubricant, gas-development agent etc.These various adjuvants can be used alone, also can two or more and use.The concrete example of such additive is for example recorded in each instructions of Japanese Patent Publication 4-69659 communique, Japanese Patent Publication 7-108928 communique, Japanese kokai publication sho 63-254149 communique, Japanese kokai publication sho 64-22904 communique etc.

< packing material >

As packing material, though be not particularly limited, can list the packing material of recording in TOHKEMY 2005-232419 communique paragraph [0158].Among these packing materials, be preferably crystallinity silicon dioxide, fused silica, rauhkalk, calcium carbonate, titanium dioxide, talcum etc.

Particularly, in the time wanting to obtain the high solidfied material of intensity with these packing materials, can add packing materials such as being mainly selected from crystallinity silicon dioxide, fused silica, silicic acid anhydride, silicate hydrate, surface treatment fine calcium carbonate, baked clay, clay and activated zinc oxide.Wherein, preferred: specific surface area (according to BET absorption method) is 50m ²more than/g, be generally 50～400m ²/ g, is preferably 100～300m ²the silicon dioxide of the Ultramicro-powder powder of/g left and right.Further preferably the silicon dioxide that hydrophobic treatments is crossed is carried out with organo-silicon compound such as organosilane, organosilazanes, diorganopolysiloxanecompositions in advance in its surface in addition.

Above-mentioned packing material can be according to object, need to use separately, also can be two or more and use.With regard to addition during with regard to use packing material, with respect to (A) composition and (B) total 100 mass parts of composition, preferably use packing material with the scope of 5～1000 mass parts, more preferably use with the scope of 20～500 mass parts, particularly preferably use with the scope of 40～300 mass parts.In the time of use level less than 5 mass parts, sometimes the fracture strength of solidfied material, breaking elongation, cementability and weather-proof cementability to improve effect insufficient, if exceed 1000 mass parts sometimes the workability of this Photocurable composition reduce.

< antioxidant >

In Photocurable composition of the present invention, can use as required various antioxidants.As these antioxidants, can list p-phenylenediamine (PPD) is that antioxidant, amine are that antioxidant, hindered phenol are antioxidant, can list phosphorous antioxidant as secondary antioxidant, and sulphur is antioxidant etc.

Though the addition of antioxidant is not particularly limited, with respect to (A) composition and (B) total 100 mass parts of composition, preferably in 0.1～10 mass parts, further preferably in the scope of 0.5～5 mass parts, use.

< plastifier >

Can in Photocurable composition of the present invention, coordinate as required plastifier.

Though be not particularly limited as plastifier, taking adjustment, the adjusting of proterties etc. of physical property as object, can enumerate the plastifier of recording as in TOHKEMY 2005-232419 communique paragraph [0173].Among them, remarkable from the reduction effect of viscosity, volatility low aspect consideration when heat-resistance test, preferred polyester is plastifier, vinyl based polymer.In addition, by adding the polymeric plasticizer as the polymkeric substance of number-average molecular weight 500～15000, the viscosity of this Photocurable composition of capable of regulating and when this Photocurable composition is solidified to the mechanical property such as pulling strengrth, length growth rate of solidfied material of gained, compared with being used as the situation of the simple plasticizer that does not contain the plastifier of component of polymer in molecule, can the initial physical property of long term maintenance, so preferably.It should be noted that, though indefinite, this polymeric plasticizer has or does not have functional group and all can.

Although the number-average molecular weight of above-mentioned polymeric plasticizer is recited as 500～15000, be preferably 800～10000, more preferably 1000～8000.If molecular weight is too low when being sometimes exposed to heat or contacting with liquid, plastifier flows out in time, can not the initial physical property of long term maintenance.In addition, if the tendency that molecular weight too highly has that viscosity uprises, workability reduces.

From the viewpoint of compatibility and weatherability, heat-resistant aging, preferred vinyl based polymer among these polymeric plasticizers.Preferred (methyl) acrylic acid series polymeric compounds among vinyl based polymer, further preferred acrylic acid series polymeric compounds.With regard to the synthetic method of this acrylic acid series polymeric compounds, can list the acrylic acid series polymeric compounds, the no-solvent type acrylate copolymer etc. that are obtained by solution polymerization in the past.Do not use solvent, chain-transferring agent because of the latter's acrylic acid series plastifier but utilize high temperature continuous polymerization (USP4414370, Japanese kokai publication sho 59-6207 communique, Japanese Patent Publication 5-58005 communique, Japanese kokai publication hei 1-313522 communique, USP5010166) to make, thus in object of the present invention more preferably.Be not particularly limited as its example, can list East Asia composite UP series and wait (with reference to industrial materials in October, 1999 number).Much less, also can list living radical polymerization as other synthetic methods.Utilize the method, because of the narrow molecular weight distribution of its polymkeric substance, can lowering viscousity so preferably, more preferably Transfer Radical Polymerization, but be not limited to this.

Though the molecular weight distribution of polymeric plasticizer is not particularly limited, preferably narrower, be preferably less than 1.8.More preferably, below 1.7, more preferably, below 1.6, more preferably, below 1.5, be particularly preferably below 1.4, most preferably be below 1.3.

The plastifier that contains above-mentioned polymeric plasticizer can be used alone, also can two or more and use, but be not necessary material.Can use as required in addition polymeric plasticizer, in dysgenic scope, also can and use simple plasticizer physical property not being produced.It should be noted that these plastifier also can coordinate in the time manufacturing polymkeric substance.

Though use consumption indefinite when plastifier, with respect to (A) composition and (B) total 100 mass parts of composition, be preferably 1～100 mass parts, more preferably 5～50 mass parts.Be difficult to show the tendency as the effect of plastifier if less than 1 mass parts has, have the tendency of the physical strength deficiency of solidfied material if exceed 100 mass parts.

< reactive diluent >

Except above-mentioned plastifier, in the present invention, can use aftermentioned reactive diluent.As reactive diluent, using such lower boiling compound that can volatilize in curing conservation, because change of shape occurs before and after solidifying, and volatile matter also causes harmful effect to environment, therefore particularly preferably boiling point is at normal temperatures 100 DEG C of above organic compounds.

As the concrete example of reactive diluent, can list 1-octene, 4 vinyl cyclohexene, allyl acetate, 1,1-diacetoxy-2-propylene, 1-methyl undecylenate, 8-acetoxyl group-1,6-octadiene etc., but be not limited to these.

With respect to (A) composition and (B) total 100 mass parts of composition, the addition of reactive diluent is preferably 0.1～100 mass parts, more preferably 0.5～70 mass parts, more preferably 1～50 mass parts.

< light stabilizer >

In Photocurable composition of the present invention, can add as required light stabilizer.The known various materials of light stabilizer, can enumerate the various materials of recording as in " antioxidant handbook ", " the deteriorated and stabilization of macromolecular material " (235～242) of CMC chemistry distribution etc. of the distribution of great achievement society, but be not limited to these.

Though be not particularly limited, but among light stabilizer, preferably ultraviolet light absorber, picture Tinuvin P, Tinuvin234, Tinuvin320, Tinuvin326, Tinuvin327, Tinuvin329 can concrete example be shown, Tinuvin213(is above Japanese vapour Ba-Jia Ji company and manufactures) etc. such such such benzophenone series, the Japanese vapour Ba-Jia Ji of Tinuvin120(company system such as triazine system, CHIMASSORB81 such as benzotriazole based compound, Tinuvin1577) etc. such benzoic ether based compound etc.

In addition, also preferred hindered amine based compound, such compound can specifically list the material of recording in TOHKEMY 2006-274084 communique, but is not limited to these.Further because the combination of ultraviolet light absorber and hindered amine based compound sometimes more can have been given play to effect, therefore though be not particularly limited and can be used together, sometimes preferably and use.

Light stabilizer can with above-mentioned antioxidant use, by and with and further given play to its effect, therefore particularly because weatherability sometimes improves particularly preferably.Can use in advance Tinuvin C353, Tinuvin B75(that light stabilizer and antioxidant are mixed to be above Japanese vapour Ba-Jia Ji company manufactures) etc.

With respect to (A) composition and (B) total 100 mass parts of composition, the consumption of light stabilizer is preferably the scope of 0.1～10 mass parts.If it is little that less than 0.1 mass parts is improved the effect of weatherability, if thereby exceed 10 mass parts does not have marked difference unfavorable in economic aspect with regard to effect.

< tackifier >

By coordinating above-mentioned tackifier, can make the cementability of the bonded object all to metal, plastics, glass etc. improve.As above-mentioned tackifier, be preferably known silane coupling agent, can enumerate as gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, gamma-amino propyl group methyl dimethoxysilane, N-(beta-aminoethyl)-gamma-amino propyl trimethoxy silicane, N-(beta-aminoethyl)-γ aminopropyltriethoxy silane, N-(beta-aminoethyl)-gamma-amino propyl group methyl dimethoxysilane, 1,3-diamido isopropyl trimethoxy silanes etc. are containing amino silanes; N-(1,3-dimethyl butylidene)-3-(triethoxysilyl)-1-propylamine, N-(1,3-dimethyl butylidene)-3-(trimethoxysilyl)-ketimide type the silanes such as 1-propylamine; γ-glycidoxypropyltrimewasxysilane, γ-glycidoxypropyl triethoxysilane, γ-glycidoxypropyl methyl dimethoxysilane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane etc. are containing the silanes of epoxy radicals; γ mercaptopropyitrimethoxy silane, γ-sulfydryl propyl group methyl dimethoxysilane etc. are containing the silanes of sulfydryl; γ-methacryloxypropyl trimethoxy silane, γ-acryloyl-oxy propyl group methyl dimethoxysilane etc. are containing the silanes of (methyl) acryloyl group; The silanes of the chloride atom such as γ-r-chloropropyl trimethoxyl silane; γ-isocyanates propyl-triethoxysilicane, γ-isocyanates propyl group methyl dimethoxysilane etc. are containing the silanes of isocyanates; Phenyltrimethoxysila,e, phenyl triethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane etc. contain the silanes of phenyl etc., but are not limited to these.In addition, can use above-mentioned containing amino silanes with above-mentioned containing silanes containing the compound of epoxy radicals, react containing the compound of isocyanate group, the compound that contains (methyl) acryloyl group, by the amino modified silanes that contains modified amido forming.

With respect to (A) composition and (B) total 100 mass parts of composition, preferably coordinate above-mentioned tackifier 0.01～20 mass parts.If less than 0.01 mass parts cementability to improve effect little, if exceed the tendency that 20 mass parts have solidfied material physical property easily to reduce.Be preferably 0.1～10 mass parts, more preferably 0.5～5 mass parts.

Above-mentioned tackifier can only use a kind, also can two or more mixing use.

< solvent >

Can in Photocurable composition of the present invention, coordinate as required solvent.As the solvent that can coordinate, can enumerate as aromatic hydrocarbon series solvents such as toluene, dimethylbenzene; The ester series solvents such as ethyl acetate, butyl acetate, pentyl acetate, cellosolve acetate; The ketone series solvents such as acetone, MEK, methylisobutylketone, diisobutyl ketone etc.These solvents can use in the time of the manufacture of polymkeric substance.

As above-mentioned photosensitizer, can enumerate as: 9,10-dibutoxy anthracene, En, perylene, cool, aphthacene, benzanthrene, phenothiazine, flavine, acridine, coumarin ketone, thioxanthone derivates, benzophenone, acetophenone, CTX, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthones or isopropyl thioxanthone etc.

Photocurable composition of the present invention can be to prepare the form of whole gradation compositions one-pack type that fitted seal forms in advance, in addition, can also be will only removing (C) photoacid generator and (F) the A liquid of the initiating agent such as optical free radical initiating agent and the form preparation of the two-component-type that B liquid that initiating agent and packing material, plastifier, solvent etc. are mixed mixed before being immediately shaped.

The solidfied material that the present invention comprises Photocurable composition.Because this solidfied material can have light-proofness and cementability, and the various characteristics excellence such as intensity, permanance, moisture-proof, therefore meet characteristic of fixing (sealing) use resin and light-shielding resin simultaneously.Solidfied material of the present invention is in the thickness of the scope of 1000 μ m, and the OD value of utilizing following mathematical expression (1) to be calculated by the transmissivity of 400～800nm is preferably more than 2.5.

OD value=-log ₁₀t(1)

(in above-mentioned mathematical expression (1), T represents the transmissivity (%) of each wavelength.）

The present invention also comprises the optical device member that comprises above-mentioned solidfied material.As optical device member, can enumerate as liquid crystal panel, sensor, optical pick-up, optical lens, LED.The present invention is particularly suitable for liquid crystal panel.

The invention still further relates to the optical device that comprises above-mentioned optical device member.As optical device, can enumerate as: various displays, digital camera, various recording medium players etc., be particularly suitable for the display modules such as liquid crystal display.

The manufacture method of display module of the present invention is to be used Photocurable composition of the present invention as feature, preferably include: the operation that is coated with above-mentioned Photocurable composition in the outer regions of the 1st member, to the Photocurable composition light irradiation of above-mentioned coating, the 1st curing process that the compound that makes above-mentioned (B) be base containing (methyl) acryloyl solidifies, the 2nd member is engaged in to the fit operation of display module of above-mentioned the 1st member after above-mentioned the 1st curing process, after above-mentioned bonding process, utilize the moisture curing of above-mentioned (A) polymkeric substance to make above-mentioned the 1st member and the bonding curing operation of the 2nd member.

Embodiment

Below enumerate embodiment the present invention is further specifically described, much less, these embodiment illustrate, and must not restrictively make an explanation.

(synthesis example 1)

Adopt aftermentioned atom transferred free radical method, the synthetic polymer B 1 with acryloxy.

By 100 parts of deoxidations of n-butyl acrylate.By the inside deoxidation of reaction vessel, add 0.42 part of cuprous bromide, deoxidation n-butyl acrylate in 4.4 parts of 20 parts, acetonitrile, 2,1.8 parts of 5-dibromo diethylene adipates 80 DEG C of mixing, add the sub-second triamine of pentamethyl two (following, referred to as triamine) 0.018 part, initiated polymerization.80 parts of remaining n-butyl acrylates are added in gradation, carry out polyreaction.In polymerization process, suitably to add triamine and adjust polymerization speed, interior temperature is adjusted into approximately 80 DEG C～approximately 90 DEG C limits by limit carries out polymerization.Monomer conversion (polyreaction rate) imports oxygen-nitrogen mixture gas when above for approximately 95% in reaction vessel gas phase portion, and limit is maintained at about 80 DEG C～approximately 90 DEG C limits by interior temperature and adds thermal agitation.Volatile ingredient decompression is removed and concentrated.It is diluted with butyl acetate, add filtration adjuvant and filter.Filtrate is added adsorbent (consonance chemical industry Kyowaad700SEN processed, Kyowaad500SH) and added after thermal agitation, filter and concentrated filtrate.Make it be dissolved in DMA, add potassium acrylate (with respect to end Br base approximately 2 molar equivalents), thermal stabilizer (H-TEMPO:4-hydroxyl-2,2,6,6-tetramethyl piperidine-n-oxygen), adsorbent (Kyowaad700SEN), at approximately 70 DEG C, add thermal agitation.Volatile ingredient is removed in decompression distillation, then, with butyl acetate dilution, adds filtration adjuvant and filters.Concentrated filtrate, obtains having the polymer B 1 of acryloxy as ultraviolet-crosslinkable group at two ends.The average acryloyl-oxy radix that the number-average molecular weight of polymer B 1 is 22500, molecular weight distribution is 1.25, import in every 1 polymer molecule is 1.9.

(synthesis example 2)

Adopt aftermentioned atom transferred free radical method, synthetic poly-(n-butyl acrylate) polymer A 1 with dimethoxy silicyl.

Under blanket of nitrogen, in 250L reactor, add CuBr(1.09kg), acetonitrile (11.4kg), butyl acrylate (26.0kg) and 2,5-dibromo diethylene adipate (2.28kg), at 70～80 DEG C, stir about 30 minutes.Add therein the sub-second triamine of pentamethyl two, initiation reaction.Start 30 minutes with within 2 hours, adding continuously butyl acrylate (104kg) from reaction.In course of reaction, suitably add the sub-second triamine of pentamethyl two, make interior temperature fade to 70 DEG C～90 DEG C.The sub-second triamine of pentamethyl two total amount using so far is 220g.Start, 4 hours, under 80 DEG C of decompressions, to remove volatile ingredient by adding thermal agitation from reaction.Add therein acetonitrile (45.7kg), 1,7-octadiene (14.0kg), the sub-second triamine of pentamethyl two (439g) also continue to stir for 8 hours.Potpourri, under 80 DEG C of decompressions, is added to thermal agitation and removes volatile ingredient.In this concentrate, add toluene, make after polymer dissolution, add zeyssatite as filtration adjuvant, add alumina silicate, hydrotalcite as adsorbent, under oxygen-nitrogen mixture body atmosphere (oxygen concentration 6%), at 100 DEG C of interior temperature, add thermal agitation.Remove by filter the solid state component in mixed liquor, filtrate, under 100 DEG C of decompressions of interior temperature, is added to thermal agitation and removes volatile ingredient.

Further in this concentrate, add alumina silicate, hydrotalcite as adsorbent, hot deterioration preventing agent, under reduced pressure, add thermal agitation (below approximately 175 DEG C of medial temperatures, degree of decompression 10Torr).Further add alumina silicate, hydrotalcite as adsorbent, add antioxidant, under oxygen-nitrogen mixture body atmosphere (oxygen concentration 6%), at 150 DEG C of interior temperature, add thermal agitation.In this concentrate, add toluene, make after polymer dissolution, remove by filter the solid state component in mixed liquor, under reduced pressure add thermal agitation filtrate and remove volatile ingredient, obtain having the polymkeric substance of thiazolinyl.This is had to polymkeric substance, dimethoxy-methyl silane (being 2.0 molar equivalents with respect to thiazolinyl), original acid A ester (being 1.0 molar equivalents with respect to thiazolinyl), the platinum catalyst (two (1 of thiazolinyl, 3-divinyl-1,1,3,3-tetramethyl disiloxane) xylene solution of platinum complex catalyst, platinum is 10mg with respect to 1kg polymkeric substance)) mix, under blanket of nitrogen, at 100 DEG C, add thermal agitation.Confirm that thiazolinyl disappears, by concentrated reaction mixture and there is endways poly-(n-butyl acrylate) polymer A 1 of dimethoxy silicyl.The number-average molecular weight of the polymer A 1 of gained is about 26000, and molecular weight distribution is that 1.3, Tg is-56.0 DEG C.With ¹hNMR analyzes and obtain the average monosilane radix importing in every 1 Molecularly Imprinted Polymer, and result is about 1.8.

(embodiment 1)

According to the mixing ratio shown in table 1, being equipped with in the flask of stirrer, thermometer, by the polymer B 1 of synthesis example 1 gained, chemical company of Light acrylate L-A(common prosperity society system, lauryl acrylate), IBXA(Osaka organic chemistry industrial group system, isobornyl acrylate), the polymer A 1 of synthesis example 2 gained, transparent (the Gen Shang industrial group system of Art-Pearl C-800, crosslinked carbamate bead, mean grain size 6 μ m) and Disparlon#6500(nanmu originally change into company's system, amide waxe) mix.By by this potpourri heating (100 DEG C), degassed, stir and within 2 hours, carry out mixing and dehydration.

After cooling, in its potpourri, add respectively and mix and blend 1, 6-hexanediyl ester, chemical industrial company of KBM-403(SHIN-ETSU HANTOTAI system, 3-glycidoxypropyltrimewasxysilane), chemical industrial company of KBM-503(SHIN-ETSU HANTOTAI system, 3-methacryloxypropyl trimethoxy silane), chemical industrial company of KBM-1003(SHIN-ETSU HANTOTAI system, vinyltrimethoxy silane), carbon black (black pigment (the solid state component 30% that Nikko bics company manufactures, DINP)), acrylic acid and chemical company of Light ester P-2M(common prosperity society system, 2-methacryloxyethyl phosphate ester acid).

Further; by adding Irgacure651(BASF Japanese firm system; 2; 2-dimethoxy-1; 2-diphenylethane-1-ketone), Darocur1173(BASF Japanese firm system; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone), Irgacure819(BASF Japanese firm system; two (2; 4; 6-trimethylbenzoyl) phenyl phosphine oxide), the triaryl sulfonium salts based compound of CPI-110TF(trifluoromethayl sulfonic acid ester), PC(Godo company system, propylene carbonate) potpourri and be uniformly mixed to prepare Photocurable composition.

Photocurable composition obtained above is carried out to following test.

1) heat-resisting creep test

Based on Fig. 2 of JIS K6859.6, on the polycarbonate plate of 75mm × 25mm × 3mm, the Photocurable composition of gained is coated with to ivb metal halide lamp (illumination: 50mW/cm in the mode that becomes 1mm thickness in the length part of counting 25mm from one end ²) light make it show cohesive 30 seconds.Afterwards, at once the fit glass plate of 75mm × 25mm × 3mm.Afterwards the 1 day time of maintenance under 23 DEG C, 50%RH, obtain tensile shear creep test sheet.Afterwards, in the calm baking oven of the temperature conditions (50 DEG C or 60 DEG C) specifying, put into test film, the weight that loads 500g on the end of a side's of test film polycarbonate carries out heat-resisting creep test under said temperature condition, measures until the time of the destruction of test film.Be displayed in Table 2 result.

2) thick film curability test

The Photocurable composition of gained is filled in to the sheet type frame of the about 2mm of thickness, ivb metal halide lamp (illumination: 50mW/cm ²) 30 seconds of light, or the light (illumination: 1000mW/cm of LED lamp (wavelength: 405nm) ², accumulated light: 1500mJ/cm ²).The 1 day time of maintenance under 23 DEG C, 50%RH afterwards.With regard to evaluation, while using metal halide lamp, be designated as above " ◎ " if solidify 1.5mm from surface, solidification range is from surface, more than 1.0mm and when the scope of not enough 1.5mm, to be designated as "○", is designated as "×" when solidification range is the scope of not enough 1.0mm from surface or when uncured.Similarly, while using LED lamp, be designated as above " ◎ " if solidify 1.0mm from surface, solidification range is from surface, more than 0.5mm and when the scope of not enough 1.0mm, to be designated as "○", is designated as "×" when solidification range is the scope of not enough 0.5mm from surface or when uncured.Be displayed in Table 2 result.

3) light-proofness test

The Photocurable composition of gained is coated in float glass plate to ivb metal halide lamp (illumination: 50mW/cm with thickness 1000 μ m ²) light make for 30 seconds it solidify.Use ultraviolet spectrophotometer, measure the transmissivity of each wavelength of transmission test body, calculate OD value according to the calculating formula of following mathematical expression (1), evaluate shielding.Be displayed in Table 3 result.It should be noted that, the composition of removing from the Photocurable composition of embodiment 5 after carbon black is also carried out to same test (experimental example 1).

OD value=-log ₁₀t(1)

It should be noted that, in mathematical expression (1), T represents the transmissivity (%) of each wavelength.

[table 1]

In table 1, respectively coordinate the use level of material to represent with g, polymer B 1 is the polymer B 1 obtaining in synthesis example 1, polymer A 1 is the polymer A 1 obtaining in synthesis example 2, other coordinate materials details with under.

The goods name that CPI-110TF:San-apro company manufactures, the triaryl sulfonium salts based compound of trifluoromethayl sulfonic acid ester.

The goods name that CPI-100P:San-apro company manufactures, 50% polypropylene carbonate ester solution of diphenyl [4-(thiophenyl) phenyl] sulphur hexafluorophosphate.

The goods name that Irgacure250:BASF Japanese firm manufactures, the potpourri of the 3:1 of iodine (4-aminomethyl phenyl) [4-(2-methyl-propyl) phenyl]-hexafluorophosphate and propylene carbonate.

LA: goods name Light acrylate L-A, chemical company of common prosperity society system, lauryl acrylate.

IBXA: Osaka organic chemistry industrial group system, isobornyl acrylate.

HDDA:1,6-hexanediyl ester.

Light ester P-2M: the goods name that chemical company of common prosperity society manufactures, 2-methacryloxyethyl phosphate ester acid.

The goods name that Irgacure651:BASF Japanese firm manufactures, 2,2-dimethoxy-1,2-diphenylethane-1-ketone.

The goods name that Darocur1173:BASF Japanese firm manufactures, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone.

The goods name that Irgacure819:BASF Japanese firm manufactures, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide.

Art-Pearl C-800 is transparent: the goods name that Gen Shang industrial group manufactures, crosslinked carbamate bead, mean grain size 6 μ m, Tg-13 DEG C.

Art-Pearl C-800 is black: the goods name that Gen Shang industrial group manufactures, the crosslinked carbamate bead of black, mean grain size 6 μ m, Tg-13 DEG C.

Art-Pearl C-400 is transparent: the goods name that Gen Shang industrial group manufactures, crosslinked carbamate bead, mean grain size 15 μ m, Tg-13 DEG C.

Art-Pearl J-4PY: the goods name that Gen Shang industrial group manufactures, PBMA(poly-n-butyl methacrylate) crosslinked bead, mean grain size 2.2 μ m.

KBM-403: the goods name that chemical industrial company of SHIN-ETSU HANTOTAI manufactures, 3-glycidoxypropyltrimewasxysilane.

KBM-503: the goods name that chemical industrial company of SHIN-ETSU HANTOTAI manufactures, 3-methacryloxypropyl trimethoxy silane.

KBM-1003: the goods name that chemical industrial company of SHIN-ETSU HANTOTAI manufactures, vinyltrimethoxy silane.

Disparlon#6500: nanmu originally changes into the goods name that company manufactures, amide waxe.

Carbon black: Nikko bics company system, black pigment (solid state component 30%, DINP).

[table 2]

[table 3]

(embodiment 2～7, comparative example 1 and 2)

Except change as shown in table 1 coordinates material, prepare similarly to Example 1 Photocurable composition, carry out each mensuration.Be displayed in Table 2 result.

As shown in table 2 and 3, the heat-resisting creep properties excellence of the Photocurable composition of embodiment 1～7, when showing excellent adhesion durability, can have light-proofness and deep curability concurrently, in giving light-proofness, can solidify by thick film.Further, as described in Example 7, by using the resin extender of black as (I) composition, further made deep curability improve.

(embodiment 8)

Use the Photocurable composition of gained in embodiment 7, utilize following method to make display module.Its process describes with Fig. 1.Herein, Fig. 1 is the side cross-sectional views that schematically shows each operation of the manufacture method of display module 10.

First, as shown in Fig. 1 (a), use spreader 20, in the peripheral region of the face of the demonstration side of back light unit 22, be coated with uncured aqueous Photocurable composition 12 to become the mode of width 2.0mm, thickness 1.2mm.

Then, as shown in Fig. 1 (b), to the layer light irradiation [illuminate condition: LED lamp (wavelength: 405nm), illumination: 1000mW/cm of the aqueous Photocurable composition 12 of coating on back light unit 22 ², accumulated light: 1500mJ/cm ²].Utilize ultraviolet lamp 24, to Photocurable composition 12 irradiation ultraviolet radiations, in making Photocurable composition 12 curing, make it show bounding force, form bonding coat 14.Utilize ultraviolet ray to irradiate, make Photocurable composition produce cohesive, because this cohesive also keeps finishing after ultraviolet ray is irradiated, therefore can after operation carry out the bonding operation of member.In addition, curing bonding coat 14 also has elasticity.

Then, as shown in Fig. 1 (c), formed the top of the back light unit 22 of bonding coat 14 from region around, liquid crystal panel 26 is declined, the lower surface peripheral region of liquid crystal panel 26 is contacted with the upper surface of bonding coat 14, back light unit 22 is engaged with liquid crystal panel 26, be assembled into display module 10.Afterwards, under 23 DEG C, 50%RH, with 1 time-of-week, bonding coat 14 is solidified and make it to become adhesive linkage 16, make display module.The thickness of adhesive linkage 16 is 1.0mm.Thus, form the interior zone 18 of the display module that back light unit 22, liquid crystal panel 26, adhesive linkage 16 surround, this interior zone 18 is in the state sealed from outside.In addition, by as above suitably getting the width dimensions W of adhesive linkage 16, interior zone 18 is by substantially from outside shading.

The display module of gained is stood up to 1500 hours at 60 DEG C and confirmed that display module does not produce skew.

Claims (13)

1. a Photocurable composition, is characterized in that, contains:

(A) in 1 molecule, on average have more than 0.8 bridging property silicyl (methyl) acrylic ester polymer,

(B) have (methyl) acryloyl shown in following general formula (1) be base containing (methyl) acryloyl be base compound,

(C) curing accelerator,

(F) optical free radical initiating agent and

(I) resin extender of mean grain size 1～150 μ m,

-OC（O）C（R ¹）=CH ₂···（1），

In described general formula (1), R ₁represent the organic group of hydrogen atom or carbon number 1～20.

2. Photocurable composition according to claim 1, is characterized in that, utilizes following mathematical expression (1), and the OD value that the transmissivity by the solidfied material of the Photocurable composition of thickness 1000 μ m under 400～800nm wavelength calculates is more than 2.5,

OD value=-log ₁₀t(1)

In described mathematical expression (1), T represents the transmissivity of each wavelength, and the unit of T is %.

3. Photocurable composition according to claim 1 and 2, is characterized in that, the resin extender that described (I) resin extender comprises black.

4. according to the Photocurable composition described in any one in claim 1～3, it is characterized in that, described (B) containing (methyl) acryloyl be the compound of base be selected from (P) main chain be not polysiloxane be the organic polymer of base containing (methyl) acryloyl, (D) there is (methyl) acrylate monomer of alkyl, (E) have polar group containing (methyl) acryloyl be the monomer of base, (G) 1 or 2 functionalities have phosphate containing (methyl) acryloyl be the monomer of base and (H) multi-functional containing (methyl) acryloyl be in the monomer of base more than a kind.

5. according to the Photocurable composition described in any one in claim 1～4, it is characterized in that, described (C) curing accelerator is photoacid generator.

6. Photocurable composition according to claim 5, is characterized in that, described photoacid generator be selected from sulfosalt and salt compounded of iodine more than a kind.

7. according to the Photocurable composition described in claim 5 or 6, it is characterized in that, described photoacid generator has and is selected from (R ¹¹sO ₂) ₂n ^-, (R ¹¹sO ₂) ₃c ^-, R ¹¹sO ₃ ^-and PF ₆ ^-in a kind of above negative ion as counter anion, wherein, R ¹¹represent alkyl, the perfluoroalkyl of carbon number 1～20 or the aryl of carbon number 6～20 of carbon number 1～20, alkyl and perfluoroalkyl can be any in straight chain, a chain or ring-type, and aryl can be unsubstituted, also can have substituting group.

8. the solidfied material of the Photocurable composition described in any one in a claim 1～7.

9. an optical device member, is characterized in that, it contains solidfied material claimed in claim 8.

10. an optical device, is characterized in that, it comprises optical device member claimed in claim 9.

11. optical devices according to claim 10, is characterized in that, it is display module.

The manufacture method of 12. 1 kinds of display modules, is characterized in that, its right to use requires the Photocurable composition described in any one in 1～7.

The manufacture method of 13. display modules according to claim 12, is characterized in that, comprising: the outer regions of the 1st member be coated with described Photocurable composition operation,

To described applied Photocurable composition light irradiation, the 1st curing process that the compound that makes described (B) be base containing (methyl) acryloyl is cured,

After described the 1st curing process, by the 2nd member be engaged in described the 1st member fit display module operation,

After described bonding process, make described the 1st member and the bonding curing operation of the 2nd member by the moisture curing of described (A) polymkeric substance.