CN1127008A

CN1127008A - UV-curable block copolymer composition

Info

Publication number: CN1127008A
Application number: CN94192754.7A
Authority: CN
Inventors: M·J·杜邦特; N·R·M·狄基泽; K·M·L·R·莫伦
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 1993-07-14
Filing date: 1994-07-12
Publication date: 1996-07-17
Anticipated expiration: 2014-07-12
Also published as: BR9407055A; NO311137B1; AU688361B2; FI960137A0; DE69413823T2; WO1995002640A1; FI960137A; ATE171972T1; DK0708802T3; AU7493294A; MX9405293A; JPH09500156A; CA2167185A1; NO960130D0; JP3420240B2; ES2122320T3; CN1067416C; NO960130L; DE69413823D1

Abstract

UV-curable block copolymer composition comprising: (a) 100 parts by weight of a block copolymer comprising at least one polymer block A derived from a monovinyl aromatic compound and at least one polymer block B derived from a conjugated diene, wherein: the content of monovinyl aromatic compound is in the range of from 5 to 50% by weight based on the total weight of block copolymer; each block A has an apparent molecular weight in the range of from 1,000 to 50,000; and each block B has an apparent molecular weight in the range of from 10,000 to 250,000; and (b) 0.5-30 parts by weight of at least one photoinitiator, characterized in that the block copolymer is a multi-armed block copolymer and at least one photoinitiator is used containing a carbonyl group which is directly bonded to at least one aromatic ring structure.

Description

The block copolymer composition of ultraviolet light polymerization

The present invention relates to a kind of UV-light (UV) solidified block copolymer composition.More particularly, the present invention relates to a kind of a kind of UV that is used for tackiness agent, sealing agent and coating and solidify block copolymer composition, wherein contain a kind of elastic block copolymer and at least a light trigger.

By the known a kind of radiation solidified rubberized basic pressure-sensitive adhesive composition of PCT application No.WO88/01281, it contains at least a elastic caoutchouc based adhesive and a kind of polythiol as linking agent.Said composition can be solidified by being exposed under electron beam irradiation or the UV radiation.Under latter event, need there be a kind of light trigger in addition.The existence of known linking agent, especially polythiol is absolutely necessary for the solidified pressure-sensitive adhesive composition that obtains having excellent adhesion performance and shear at high temperature performance.

Yet owing to economic and processing reason, it is attractive reducing component quantity and still obtaining a kind of curable adhesive composition that has and at high temperature have superperformance.

U.S. patent No.5,093,406 discloses a kind of pressure-sensitive adhesive that contains a kind of radically curing product, this cured product be by the mixture that contains following ingredients with preparing as UV solidified method:

(a) a kind of unsaturated elastic body component of 15～60 parts of weights (pbw) suitably contains the two blocks of vinylbenzene-isoprene and vinylbenzene-isoprene-styrene triblock copolymer,

(b) a kind of hydrogenated styrene base tackifying resin of 85～40pbw,

(c) 0～15pbw a kind of strengthen resin be used for elastomeric component the polyethylene end-block and

(d) a kind of polythiol linking agent of 0～10pbw.

Although the existence of polythiol linking agent is chosen wantonly, only put down in writing the composition that contains the polythiol linking agent obviously in the embodiment preferred, for example this point is easy to find out from embodiment.

Therefore, still need the UV curing composition, said composition does not need the existence of agent in parallel and effectively solidifies and can for example suitably use in the hot-melt adhesive composition.

The rubber-based hot melt tackiness agent, sealing agent and the coating composition that do not contain any linking agent usually need be in oxygenous the least possible air sets.Be exposed under the UV irradiation promptly, the aliphatic double bond in the rubber will be opened and form free radical.The different rubber polymer chains that contain free radical reach needed crosslinked by said free radical along the polymer chain interaction result.Yet, the also easy and oxygen reaction generation superoxide of free radical.The formation of known such superoxide seriously hinders crosslinking reaction.Therefore, being solidificated in the rare gas element of rubber-based composition that does not conform to any linking agent can be carried out optimum in nitrogen easily.This just is appreciated that the UV solidified industrial prospect that the requirement of lacking the oxygen air has seriously been hindered the rubber-based hot melt tackiness agent, sealing agent and the coating that do not contain linking agent.

Therefore, can be very favourable in atmosphere if UV solidifies, wherein the oxygen of Cun Zaiing from a small quantity to normal content, as, from 1 volume % to air the normal value of about 21 volume %.From commercial and economic viewpoint, operation in the abundant relatively air of oxygen and do not need expensive equipment and concrete sfgd. to guarantee that oxygen-free gas air is very attractive.

Therefore, an object of the present invention is to provide a kind of block copolymer composition, said composition is by being exposed under the UV irradiation and not using any linking agent to solidify effectively.In addition, an object of the present invention is to provide a kind of UV solidification heat melt adhesive, sealing agent or coating composition, said composition is without any need for the existence of linking agent and be easy to be cured in oxygenous air.

Therefore, the present invention relates to a kind of UV and solidify block copolymer composition, wherein contain:

(a) segmented copolymer of 100 parts of weights (pbw) wherein contains at least a polymer blocks A and at least a polymer blocks B that is generated by conjugated diene that is generated by monovinyl aromatic compounds, wherein,

---the content range of monovinyl aromatic compounds is 5～50% weight of segmented copolymer gross weight;

---the apparent molecular weight scope of each block A is 1,000～50,000; With

The apparent molecular weight scope of-each B block is 10,000～250,000; With

(b) 0.5～30pbw, at least a light trigger of preferred 5～20pbw, said composition is characterised in that this segmented copolymer is a kind of higly branched chain segmented copolymer and uses a kind of light trigger that contains a carbonyl at least, direct and at least one the aromatic ring structure bonding of this carbonyl.

The saying of " apparent molecular weight " that this specification sheets is used refers to and uses the molecular weight of polystyrene calibration criterion by gel permeation chromatography.

The segmented copolymer that is suitable as component in the composition (a) according to the present invention can be any segmented copolymer that meets above-mentioned requirements in principle.Then the segmented copolymer of Shi Heing comprises (AB) nX that has general molecular formula, (BA) nX, (ABA) nX, (BAB) the symmetrical higly branched chain segmented copolymer of any structure and asymmetric or symmetrical higly branched chain segmented copolymer among the nX with structure of general formula (AB) p (Bq) X, A and B as defined above, n represents integer more than 2 or 2 and preferred 2～20, p and q represents the integer also preferred 1-3 more than 1 or 1, these values depend on the functionality of used coupling agent, and wherein the coupling agent residue is represented with X.Coupling agent such as Vinylstyrene, silicon tetrachloride, γ-glycidoxypropyl-propyl group-trimethoxy-silane and ethylene dibromide commonly used.The segmented copolymer that preferably has general formula (AB) nX, A and B such as preceding definition, n represents 3～20 integer, and is preferred 4-12, and X represents the coupling agent residue, preferred divinyl phenyl residue.Use any conventional coupling technology to make the active intermediate polymer chain coupling of order preparation prepare this higly branched chain segmented copolymer, such as in U.S patent Nos.3,231,635; 3,431,323; 3,251,905; 3,390,207; Disclosed technology in 3,598,887 and 4,219,627.

Monovinyl aromatic compounds can be selected from vinylbenzene, α-vinyl toluene, neighbour-vinyl toluene, right-vinyl toluene, right-t-butyl styrene, 1,3-dimethyl styrene or its mixture, wherein vinylbenzene most preferably.

The suitable conjugated diene that is used for the segmented copolymer of component (a) is 1,3-divinyl, 2-methyl-1,3-divinyl (isoprene), 2,3-dimethyl-1,3-divinyl, 1,3-pentadiene, 1,3-hexadiene or its mixture, wherein preferred monomers is 1,3-divinyl, isoprene or its mixture.Isoprene most preferably.

Pointed out that as mentioned preferred segmented copolymer is a kind of higly branched chain vinylbenzene (S)-isoprene (I) or vinylbenzene-divinyl (B) segmented copolymer, wherein the styrene content scope is 5～25% weight.The example of commercially available a kind of higly branched chain S-I segmented copolymer is KRATON D-1320X (KRATON is a trade mark).

Can be according to light trigger component (b) in the block copolymer composition of the present invention and form by the combination of one or both or multiple light trigger.In any case at least a in the used light trigger must be a kind of compound that contains a carbonyl, direct and at least one the aromatic ring structure bonding of this carbonyl.This light trigger preferably from:

(1) a kind of benzophenone with general formula (I) optional combines with at least a tertiary amine.

R wherein ¹-R ⁸Represent hydrogen respectively or have the alkyl of 1-4 carbon atoms, preferable methyl, R ⁷And/or R ⁸Also represent the alkoxyl group of 1-4 carbon atoms in addition, the n value is 0,1 or 2.

(2) at least a sulfur-bearing carbonyl compound, wherein carbonyl directly with at least one aromatic ring bonding mutually, preferably have general formula (II):

R wherein ⁹, R ¹⁰, R ¹¹Represent respectively the alkyl of hydrogen, 1-4 carbon atoms or 1-4 carbon atoms the sulfane base and

(3) mixture of (1) and (2).

The example of the suitable compound of (1) class is a benzophenone, 2,4,6-trimethylammonium benzophenone, 4-methyldiphenyl ketone and 2,4,6-trimethylammonium benzophenone and 4-methyldiphenyl ketone (ESACURE TZT) and 2, the meltable mixture of 2-dimethoxy-1,2-diphenylethane-1-ketone (IR-GACURE 651) (ESACURE and IRGACURE 651 are trade marks).These compounds can be used in combination with tertiary amine, as UVECRYL 7100 (UVE-CRYL is a trade mark).

The compound that (2) class comprises is as 2-methyl-1[4-(methylthio group) phenyl]-2-morpholino acetone-1, IRGACURE 907 has commercially available (IRGACURE is a trade mark).

The mixture that the mixture that the example of suitable mixture ((3) class) is made up of 15% weight, 2-isopropyl thioxanthone and 4-isopropyl thioxanthone and 2,4,6-trimethylammonium benzophenone of 85% weight and 4-methyldiphenyl ketone are formed is prepared.This mixture has commercially available, and trade mark is called ESACURE X15.

Above (1), the light trigger in (2), any class of (3) class also can be used in combination with other light trigger such as UVECRYL P115.Benzophenone and said UVE-CRYL P115 combine and are particularly useful.

Light trigger is selected from (i) benzophenone in the preferred embodiment of the invention; (ii) benzophenone and contain the mixture of the tertiary amine of a carbonyl, this carbonyl are directly and at least one aromatic ring bonding and (iii) 2-methyl-1-[4 (methylthio group) phenyl]-2-morpholino acetone-1.2-methyl-1-[4-(methylthio group) phenyl]-2-morpholino acetone-1 most preferably wherein.

The consumption of light trigger is that the segmented copolymer (phr) of 0.5～30 part of heavy/100 part weight is to guarantee to be exposed to full cross-linked under the UV irradiation.Preferred 5-the 20phr of light trigger consumption.

Being used for the crosslinked UV irradiation of block copolymer composition of the present invention can be to have any UV of output signal spectrographic source in principle, and this spectrum has one or more peaks between 200～500 nanometers (nm) wavelength.Specially suitable UV source is Fusion lamp (Fusion is a trade mark), and it has maximum output valve at 260-270nm, 320nm and 360nm (" H " type lamp), 350-390nm (" D " type lamp) or when 400-430nm (" V-type lamp ").Also these Fusion lamps can be used in combination.H and D lamp (300 watts/inch promptly 120 watts/centimetre of linear heat generation rates) are particularly useful, yet the combination of D type lamp and H type lamp also can suitably be used.

Can carry out the UV irradiation with any known method.A kind of suitable method as with sample one with the layer of heat fusing gained or in a layer, be exposed under the UV irradiation by the solvent coating gained, under the UV source, (represent with a meter per minute, m/min) allow sample pass through with certain speed.If desired, can repeat the exposure irradiation of one or many, as allow repeatedly sample under the UV source by or allow sample under two or more lamps that order is placed, pass through, to reach sufficient curing.Total radiation dose is low more and speed is high more, can be at sample under this speed by obtaining abundant and gratifying curing under the UV source, and the ability to cure of said sample is also good more.

Solidify block copolymer composition according to UV of the present invention and can suitably be applied to heat fusing and solvent cement composition, sealing agent and coating.When being used for binder composition, also can contain common additives, as tackifying resin, softening oil and oxidation inhibitor.For example, suitable hot-melt adhesive composition can contain except block copolymer composition of the present invention:

At least a resin of (c) 10-300 parts heavy/100 parts section of repointing multipolymers (phr), it is compatible with poly-(conjugated diene) polymer blocks;

(d) softening agent of 0-150phr; With

(e) oxidation inhibitor of 0.5-5phr

Poly-(conjugated diene) Compatibilized resin that is fit to is tackifying resin and liquid resin, such as polyterpene resin, inden resin, rosin ester, staybelite, α-pinene resin, β-pinene resin, the hydrocarbon resin that derives from oil and resol.REGALITE R91 for example, R101, R125 and S260 (REGALITE is a trade mark), ESCOREZ 1310 and 5380 (ESCOREZ is a trade mark), WINGTACK 95 (WINGTACK is a trade mark), FORAL 85 and 105 (FORAL is a trade mark), PICCOLYTE A115, S115 and S10 (PICCOLYTE is a trade mark) and PICCOTAC 95E.The low unsaturated polyester of preferred use, such as REGALITE R91, R101 or R125.

Naphthenic oil and paraffin oil or low-molecular-weight polybutylene polymer can be used as softening agent mineral oil.The example of suitable manufacturing methods is SHELLFLEX 371 and 451 and TUFFLO6204 (naphthenic oil), TUFFLO 6056 (paraffin oil) and polybutene HYVIS 200, NAPVIS 30 and NAPVIS D-10.SHELLFLEX, TUFFLO, HYVIS and NAPVIS are trade marks.REGALREZ 1018 (REGALREZ is a trade mark), ON-DINA 68 (ONDINA is a trade mark) and V-OIL 7047 (V-OIL is a trade mark) are also very suitable.

Any oxidation inhibitor commonly used in the adhesive formula can be used as component (e).The example of this oxidation inhibitor is phenolic compound IRGANOX 1010 (IRGANOX is a trade mark).

Except component (c), (d) with (e), also can contain other additive, as end-block Compatibilized resin, UV stablizer, filler, fire retardant and analogue, depend on the employed actual conditions of hot-melt adhesive composition.

Hot-melt adhesive composition, encapsulant composition and coating composition also form a part of the present invention, wherein contain the UV that had said the front and solidify block copolymer composition.Same application is by being exposed to said tackiness agent, sealing agent and coating composition the curing composition that obtains under the UV irradiation.

The following examples have further proved the present invention, yet are not that scope of the present invention is confined within these specific embodiments.

Light trigger abbreviation used among the embodiment is as follows:

TZT：ESACURE?TZT????I184：IRGACURE?184

X15：ESACURE?X15????I651：IRGACURE?651

P115：UVECRYL?P115??I907：IRGACURE?907

UVEC:UVECRYL 7100 Benz: benzophenone

Except as otherwise noted, sample is exposed in the nitrogen unhurried current simultaneously with the irradiation of UV source.This nitrogen gas stream still contains oxygen in irradiation process.Therefore, shine during at oxygen content up to 10 volume %.Embodiment 1

The composition that contains a kind of higly branched chain S-I segmented copolymer, two kinds of polyisoprene Compatibilized resins and a kind of oxidation inhibitor prepares by following material is closely mixed:

KRATON D-1320X of 100pbw,

150phr?REGALITE?R91

60phr REGALREZ 1018 and

1phr?IRGANOX?1010

KRATOIV D-1320X is the higly branched chain segmented copolymer of a kind of S of containing-I segmented copolymer side chain.Used coupling agent is a Vinylstyrene.The polystyrene that wherein contains 10% weight.The apparent molecular weight of each S-I side chain approximately is 100,000 and the maximum molecular weight of each polystyrene block approximately is 11,000.The sum of side chain from 6 to 100 does not wait; Normally 6～40.

Add several light triggers in this prescription, the composition with gained like this is exposed under the UV irradiation afterwards, with 5 meters/minute speed allow composition with the heat fusing form at single Fusion D type lamp (F300; 300 watts/inch, promptly 120 watts/centimetre) under pass through.Measure the adhesion shear fracture temperature (SAFT) of these compositions.The above value of 140 ℃ or its is qualified.The results are shown in the Table I.

Table I

The UV of several compositions solidifies

Light trigger (pbw) TZT X15 I651 I184 UVEC adhesion shear fracture temperature (℃)

Pass through 2 times 5 110＞16010＞160＞160 by 1 time

5????????????????????????????114????＞160

10＞160＞1,603 2 10＞160＞1,605 5 151＞1,603 3 137 1,405 10＞160＞16,010 10＞160＞160 be clear that very much under D type UV lamp by 2 times by table 1 after all prescriptions all shown good SAFT value; (300 watts/inch namely 120 watts/centimetre) however have 5 kinds of prescriptions only after 1 time, to show good SAFT value, namely＞160 ℃. Embodiment 2

The prescription that major ingredient used among the embodiment 1 is identical is used for evaluating the influence to the SAFT value of speed that prescription is passed through under different UV source.Used light trigger is IR-GACURE 907, and consumption is the 5pbw/100pbw segmented copolymer.Place (that is: D+V, D+H and D+D) successively when two lamps, being radiated in the air under second lamp carried out, so do not use nitrogen gas stream.The results are shown in the Table II; Listed SAFT value is ℃ to provide.

Table II with friction-motion speed with in the SAFT value of carrying out under the different UV lamps after UV solidifies

D type+D type+D type+speed D type lamp H type lamp ^*︱ V-type lamp D type lamp (rice/minute) pass through 1 time by 1 time 5＞160＞160＞160＞160＞16,010 112＞160＞160＞160 12,315 104 131＞160 118 10,520 97 106 156 104 98 by 2 times by 1 time by 1 time ^*To be 300 watts/inch (120 watts/centimetre) showed good effect for the combination of H type lamp to the linear heat generation rate of H type and V-type lamp after Table II is clear that especially D type lamp very much, even under 20 meters/minute high speed.

Also measure the characteristic adhesion property (hang down ring viscosity (loop tack) and peel adhesion) of the identical irradiation sample of listing among Table III and the IV.

Table III

The ring viscosity of hanging down: the influence of lamp and speed (ox/25 millimeter)
								Speed (rice/minute)	D type lamp (1 lamp)				D type+H type lamp	D type+D type lamp
By 1 time		By 2 times		By 1 time	By 1 time				D type lamp (1 lamp)				D type+H type lamp	D type+D type lamp
By 1 time		By 2 times		By 1 time	By 1 time		Have		Do not have	Have	Do not have	Have	Have	Do not have
????5 ????10 ????15 ????20	????26 ^????27 ????25 ^????25 ^*	????28 ????- ????26 ^*????-	????26 ????25 ????24 ????22	????25 ????- ????24 ^*????-	????23 ????21 ????26 ????23	????21 ????26 ????22 ????24	Have		Do not have	Have	Do not have	Have	Have	Do not have	????21 ????- ????- ????-

" have ": refer to have low speed N ₂Stream, " nothing ": refer to that sample solidifies (no N in the open ₂Stream) *: crossed grid viscosity (zippery tack)

Table IV

Top layer peel adhesion: the influence of lamp and speed (ox/25 millimeter)
								Speed (rice/minute)	D type lamp (1 lamp)				D type+H type lamp	D type+D type lamp
By 1 time		By 2 times		By 1 time	By 2 times				D type lamp (1 lamp)				D type+H type lamp	D type+D type lamp
By 1 time		By 2 times		By 1 time	By 2 times		Have		Do not have	Have	Do not have	Have	Have	Do not have
????5 ????10 ????15 ????20	????19 ????20 ^*????17 ????16	????19 ????- ????19 ????-	????16 ????18 ????19 ????20	????17 ????- ????18 ????-	????17 ????17 ????16 ????21	????19 ????19 ????17 ????19	Have		Do not have	Have	Do not have	Have	Have	Do not have	????19 ????- ????- ????-

Can think that by these tables curing does not damage adhesion property.Embodiment 3

Use with embodiment 2 in used identical prescription and use and situation without nitrogen gas stream under be exposed under the Fusion H type lamp (F300) and shine.With prescription with different speed once with twice under the H type lamp by and under two H type lamps placing successively by exposing irradiation.Each by back mensuration SAFT value (with a ℃ expression).The results are shown in the Table V.

Table V is used and is passed through 2 times by 1 time without 2 lamps of 1 lamp of SAFT value speed (meter/minute) after the UV curing of nitrogen gas stream by 1 time

Having or not nothing 5 173 166 174 169 17,210 146 159 160 159 15,515 106 108 137 152 16,720 88 85 107 101 117 can push away human relations by Table V shines in air, promptly do not use nitrogen gas stream, produced good SAFT value, this value is similar with the SAFT value that exposes use nitrogen gas stream gained between the light period, in some cases even better.Embodiment 4

Several light triggers and light trigger combination are joined in the basic recipe used among the embodiment 1.With the composition of gained like this (A-G) with 5 meters/minute speed three times (1p, 2p, 3p) under a Fusion D type lamp by making its curing.At every turn by after measure the SAFT value of some compositions, 95 ℃ pull-out capacity (HP95 ℃) and 180 ° of top layer peel adhesion.The results are shown in the Table VI.

Table VI

The UV hardening composition A B C D E F GBenz 55 10 10 5 10I,651 5 5UVEC 10P115 10I,907 5 of block copolymer composition

1p?????150????148???157????133????155??＞160??141???SAFT(℃)2p???＞160??＞160???158??＞160??＞160??＞160??147

3p???＞160??＞160???159??＞160??＞160??＞160??151

1p???＞100??＞100?＞100??＞100?????????＞100

HP?95℃2p???＞100??＞100?＞100??＞100?????????＞100

° top layer, 3p＞100＞100＞100＞100＞100180 stripping 1p 20 18 16 19 16 16 10 from clinging power 2p 18 20 21 21 16 15 12 (ox/25 millimeter) 3p 21 20 18 22 17 16 13 by Table VI as can be seen especially UV solidified binder composition A-F showed good adhesion property.

Embodiment 5

With another kind of UV lamp is that H type light irradiation is tested the prescription that contains following component:

KRATON?D—1320X?????100phr

REGALITE?R91????????150phr

REGALREZ?1018???????60phr

IRGACURE?907????????5phr

IRGANOX?1010????????1phr

This lamp is launched general hg spectrum significantly.

Resulting SAFT test result is listed in Table VII.

Table VII

The influence of SAFT:H type lamp (℃) 2 lamps of 1 lamp of speed (rice/minute) pass through 1 time by 2 times by 1 time

Having or not does not have 5 171 167 171 169 16,810 145 148 164 155 147

＞160?＞16015?????????99????107???137???152??＞16020?????????88?????85???107???101????112

Table VII N as can be known thus ₂Optional and to several head of the curing efficiency of this prescription without any influence.In addition, seem that be possible (SAFT be higher than 150 ℃) by having good curing efficiency with twice of the speed up to 15 meters/minute under H type lamp.

The adhesion property of these styles has also recorded and has been listed among Table VIII and the IX.

Table VIII

The ring viscosity of hanging down: the influence of H type lamp (ox/25 millimeter)
	2 lamps of 1 lamp of speed (rice/minute) nothing had or not by 2 times by 1 time by 1 time
5?????????25?????23??????15 ^????18????21 10????????24?????25??????24??????24????21 15????????24?????23??????23??????25????23 20????????23?????20 ^????20??????20????21 ^*
	*-crossed grid sticky table IX
Top layer peel adhesion: the influence of H type lamp (ox/25 millimeter)	*-crossed grid sticky table IX
	2 lamps of 1 lamp of speed (rice/minute) nothing had or not by 2 times by 1 time by 1 time
5????????20????20?????17???????18??????16 10???????18????18?????17???????18??????16 15???????19????20?????16???????16??????19 20???????19????21?????20???????22??????19

Result by the front can find out that regardless of curing speed or dosage adhesion property is not subjected to solidify and damages.

Embodiment 6

Use a similar prescription (KRATON D-1320X/REGALITE R91/REGALREZ 1018/IRGANOX 1010; 100/150/60/1), wherein with benzophenone and EBECRYL 7100 (or UVECRYL 7100: the two all is the trade name of identical product) in conjunction with as light trigger.Sample is shone under H type lamp with different speed.Heatproof result's (pull-out capacities under SAFT and 95 ℃) lists among Table X and the XI:

Table X

SAFT: the impact of curing rate (℃) 5 m/mins 10 m/mins 15 m/mins 20 m/mins of adjusted component benzophenone EBECRYL are by by by by by by by by 1 time 2 times 1 time 2 times 1 time 2 times 1 time 2 times
	10????10?????156???163?????154????158????92????159??111??130 5?????10?????155???169?????159????-??????97????105 ^95???108 ^

*=crossed grid viscosity

Table X I

95 ℃ of HP: the influence of curing speed (hour) 1 kilogram of 1 kilogram of 500 gram of 5 meters/minute 10 meters/minute 15 meters/minute 1 kilogram of 500 grams of 1 kilogram of 500 gram of 20 meters/minute 500 grams of adjusted component benzophenone EBECRYL
	10 10 pass through 1 time＞100 6 0.07 by 2 times＞100 61＞100 77 15

Be clear that very much with benzophenone and tertiary amine in conjunction with also obtaining good curing efficiency in the open by these data as light trigger.

Embodiment 7

1. test has two kinds of irradiation curing block copolymer mixtures (A and B) of (SB) mBnX molecular structure, m+n=4 wherein, other mean value of the branch of m and n all is approximately 2, wherein X represents the tetrachloro silicane residue, uses the application to relate to promptly respectively: 907 two kinds of light triggers of IR-GACURE 651 and IRGACURE carry out " in the open " irradiation to be tested.

The further details of these polymkeric substance is listed in Table X II

Table X II polymer A B% polystyrene 12.7 10.8% vinyl 54 56CE 96 95 vitrification points-59 ℃-56 ℃ of melt flow ratio 8.1 1.4 adhesive compositions (3) (4) (5) (6) polymer 100phr 100REGALITE 91 147 129REGALEZ 1,018 63 81IRGACURE 651 3 3IRGACURE 907 3 3IRGANOX 1,010 22

Under the D of a F-300 type lamp, sample is solidified with friction-motion speed.These adhesive formulas are being used low speed N ₂Shine under the situation of stream and directly curing.The results are shown in Table X III.

Table X III

Speed (rice/minute)	Composition (3)		Composition (4)		Composition (5)		Composition (6)
	Composition (3)		Composition (4)		Composition (5)		Composition (6)		By 1 time	By 2 times	By 1 time	By 2 times	By 1 time	By 2 times	By 1 time	By 2 times
	????5 ????10 ????15 ????20	??＞160 ????79 ????69 ????72	????135 ????80 ????75 ????74	??＞170 ????81 ????76 ????78	＞170 ＞160 ??86 ??81	??＞170 ????89 ????84 ????83	??＞170 ??＞160 ????86 ????81	??＞160 ????85 ????75 ????74	By 1 time	By 2 times	By 1 time	By 2 times	By 1 time	By 2 times	By 1 time	By 2 times	??＞160 ????96 ????75 ????77

2. do not use any nitrogen gas stream then, with more high-power lamp test polymer A and the B of (SB) mBnX that has formula are solidified with higher speed.

Two components in the test composition, be light trigger IRGACURE 651 and 907, contain in the said composition with Table X II in other identical component of listing, promptly fill a prescription 4 use IRGACURE 651 as light trigger based on the A polymkeric substance, prescription 5 uses IR-GACURE 651 as light trigger based on the B polymkeric substance, fill a prescription 6 use IR-GACURE 907 as light trigger based on B.

Irradiation by Fusion F-600 lamp is directly solidified all samples.

The results are shown among Table X IV and the XV.

Table X IV

Speed (rice/minute)	D type lamp			H type lamp
	D type lamp			H type lamp			????4	????5	????6	????4	????5	????6
	?0 ?10 ?20 ?25 ?30 ?40 ?50	????75 ??＞170 ????77 ????90 ????80 ????74 ????76	????80 ??＞170 ??＞170 ????153 ????105 ????86 ????86	????＞170 ????＞170 ????＞170 ????＞170 ??????141 ??????95	????75 ??＞170 ????170 ????166 ????95 ????86 ????77	??????80 ????＞170 ????＞170 ????＞170 ????＞170 ??????118 ??????92	????4	????5	????6	????4	????5	????6	＞170 ＞170 ＞170 ＞170 ＞170 ??127

The SAFT result of solidified sample under the lamp of a F-600 (℃)

Table X V

Speed (rice/minute)	D type+D type lamp		D type+H type lamp
	D type+D type lamp		D type+H type lamp			????4	??5	????4	??????5	??????6
	0 20 30 40 50 60	????75 ??＞170 ??＞170 ????111 ????82 ????80	??80 ＞170 ＞170 ＞170 ??114 ??110	????75 ??＞170 ????150 ????106 ????86 ????84	??????80 ????＞170 ????＞170 ??????147 ????＞170 ????＞170	????4	??5	????4	??????5	??????6	????＞170 ????＞170 ????＞170 ????＞170 ????＞170

The SAFT result of solidified sample under F-600 lamp group (℃)

Can know that the result is improved when using IRGACURE 907 light triggers.Use the prescription of D and H type lamp combination irradiation B polymer-based carbon to obtain best result.In this case, when 60 meters/minute speed, can access unexpectedly and be higher than 170 ℃ SAFT result! This is that the highest speed that once reached is solidified in irradiation.

Pull-out capacity (HP) in the time of 95 ℃: 1 kilogram

The sample of only selecting to have good heat resistance carries out HP95 ℃ of test, and VI is listed as Table X.

Table X VI

Speed (rice/minute)	D type lamp			H type lamp
	D type lamp			H type lamp			4 (hour)	5 (hour)	6 (hour)	4 (hour)	5 (hour)	6 (hour)
	?10 ?20 ?25 ?30 ?40	＞100 ??- ??- ??- ??-	???＞100 ???＞100 ?????- ?????- ?????-	???＞100 ???＞100 ???＞100 ???＞100 ?????-	????＞100 ????0.5/12.5 ????0/42 ????0 ????-	????＞100 ????＞100 9.5/＞100 ????＞100 ??????-	4 (hour)	5 (hour)	6 (hour)	4 (hour)	5 (hour)	6 (hour)	????＞100 ????＞100 ????＞100 ????＞100 ??????8.6

Pull-out capacity result under 95 ℃ of solidified sample under F-600 lamp

Table X VII

Speed (rice/minute)	D type+D type lamp		D type+H type lamp
	D type+D type lamp		D type+H type lamp			4 (hour)	5 (hour)	4 (hour)	5 (hour)	6 (hour)
	?20 ?30 ?40 ?50 ?60	???＞100 ???＞100 ?????- ?????- ?????- ?????	???＞100 ???＞100 ???＞100 ?????- ?????- ?????	????＞100 ?19/＞100 ??????- ??????- ??????- ????	???＞100 ???＞100 ???＞100 ???＞100 ???＞100	4 (hour)	5 (hour)	4 (hour)	5 (hour)	6 (hour)	＞100 ＞100 ＞100 ＞100 ＞100

Pull-out capacity result under 95 ℃ of solidified sample under the combination of F-600 lamp

We can see the good temperature performance (HP95 ℃＞100 hours) of test polymkeric substance when using IRGACURE 907 light triggers once more at this.IRGACURE907 makes and has reached higher curing speed.

Can be known under the situation that oxygen exists by the embodiment of front does not need N ₂It is possible flowing and effectively solidifying.At a high speed be issued to high curing efficiency and heat resistance is possible.

Embodiment 8

(i) five kinds of standard irradiation photosensitive compositions of preparation, the segmented copolymer that among the Table X VIII every kind contains poly-(vinylbenzene) and poly-(divinyl) block of listing in that wherein contains 100 parts of weights, the photosensitizers IRGACURE 651 of 1 part heavy oxidation inhibitor IRGANOX 1010 and 2 parts heavy.

Last a kind of segmented copolymer listed in the table does not conform to the invention of claim, has been listed as this example of opposing.

Table X VIII polymer features

S block S-B embedding block total molecule amount segment molecule amount total molecular weight molecular form polyphenyl second vinyl polymers (x1000) (x1000) (x1000) alkene content (1,2-add

Become) content A 10.7 71 276, (SB) 2B2 12.7 54B 11.2 87 339, (SB) 2B2 10.8 56C 10.7 81 222, (SB) 2B2 12.5 60.5KRATON D 13 330, (SB) 3.5 21+/-51116 Comparative Examples, 12 45 91 SBS 40+/-5

The film for preparing 22 micron thickness by these five kinds of photosensitivity phase compounds by the casting mode from solvent-based formulas (40%, in the toluene).

With film with 5 meters/minute speed respectively 1 time and 2 times under a Fusion D type lamp by shining, and gel content is analyzed.

Table X IX irradiation back gel percentage polymkeric substance passes through 2 A 59.5 85.5B 81.0 86.9C 73.8 87.5KRATON D 1,116 31.7 70.4 Comparative Examples 0.3 9.6 by 1 time

(ii) photo-sensitive composition prepares with the photosensitizers IRGACURE 651 of different amounts from segmented copolymer (100 parts of weights), the IRGANOX 1010 (1 part of weight) of the alleged A of work in front, and X is listed as Table X.

Film by these preparation of compositions 22 micron thickness also shines film as described in embodiment 8 (i).Measure postradiation gel percentage ratio.

The postradiation gel of Table X X (%)

Composition segmented copolymer/AO/PS passes through 2 times by 1 time
	?100/1/1?????????????46.2????????73.3 ?100/1/2?????????????59.5????????85.5 ?100/1/4?????????????84.7????????93.7

Claims

1.UV the curing block copolymer composition, it contains:

(a) a kind of segmented copolymer of 100 parts of weights wherein contains at least a polymer blocks A and at least a polymer blocks B that is generated by conjugated diene that is generated by monovinyl aromatic compounds, wherein:

---the monovinyl aromatic compounds content range is 5-50% weight of segmented copolymer gross weight;

---the apparent molecular weight scope of each block A is 1,000～50,000; With

---the apparent molecular weight scope of each B block is 10,000～250,000; With

(b) at least a light trigger of 0.5-30 parts of weights is characterized in that segmented copolymer is a kind of higly branched chain segmented copolymer and uses a kind of light trigger that contains a carbonyl at least, direct and at least one the aromatic ring structure bonding of this carbonyl.

2. according to the composition of claim 1, the monovinyl aromatic compounds content range that it is characterized in that the higly branched chain segmented copolymer is 5-25% weight.

3. according to claim 1 or 2 and composition, it is characterized in that segmented copolymer have general formula (nX of A-B), wherein n is the integers in 3-20 scopes, X is the coupling agent residue.

4. according to each composition in the claim 1-3, it is characterized in that monovinyl aromatic compounds is a vinylbenzene and conjugated diene is isoprene, 1,3-divinyl or its mixture.

5. according to the composition of claim 4, it is characterized in that conjugated diene is an isoprene.

6. according to each composition in the claim 1-5, it is characterized in that component (b) comprises at least a light trigger, this light trigger is selected from:

(1) at least a benzophenone with general formula (I) optional combines with at least a tertiary amine,

R wherein ¹To R ⁸Represent hydrogen respectively or have the alkyl of 1-4 carbon atoms, wherein R ⁷And/or R ⁸Represent the alkoxyl group of 1-4 carbon atoms, the n value is 0,1 or 2,

(2) at least a sulfur-bearing carbonyl compound, wherein direct and at least one the aromatic ring bonding of carbonyl preferably has formula II structure,

(3) mixture of (1) and (2)

7. according to the composition of claim 6, wherein light trigger is selected from the mixture, 2 of benzophenone, benzophenone and a kind of tertiary amine, 4,6-trimethylammonium benzophenone, 4-methyldiphenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-ketone and 2-methyl-1-[4-(methylthio group) phenyl]-2-morpholino acetone-1 and composition thereof.

8. according to the composition of claim 7, wherein light trigger is 2-methyl-1-[4 (methylthio group) phenyl]-2-morpholino acetone-1.

9. hot-melt adhesive composition that contains each block copolymer composition in the with good grounds claim 1-8.

10. encapsulant composition that contains each block copolymer composition in the with good grounds claim 1-8.

11. coating composition that contains each block copolymer composition in the with good grounds claim 1-8.

12., promptly under the condition that air exists, said composition is exposed under the UV and shines according to the curing of each composition in the claim 9-11.

13. curing composition that obtains by the method for claim 12.