JP5308564B1 - Two-part curable polyorganosiloxane composition and use thereof - Google Patents

Abstract

The present invention provides a curable polyorganosiloxane composition excellent in rapid curability.
(A) An alkenyl group-containing polyorganosiloxane containing two or more alkenyl groups in the molecule; (B) a polyorganohydrogensiloxane having two or more hydrogen atoms bonded to a silicon atom in the molecule. The ratio of the number H _B of hydrogen atoms bonded to the silicon atom in (B) to the number Vi _A of alkenyl groups in (A) comprising a platinum-based catalyst is 0.5 to 10.0; (C) is a two-component curable polyorganosiloxane composition comprising a first component and a second component, which is 0.5 to 2000 ppm as a platinum-based metal atom, wherein the first component is (A ) And (C), and the second component contains (B), a two-part curable polyorganosiloxane composition.
[Selection figure] None

Description

  The present invention relates to a curable polyorganosiloxane composition, and more particularly, to a two-part curable polyorganosiloxane composition having fast curability and a method for producing an adhesive using the same.

  In a display device such as a mobile phone provided with a display component such as a liquid crystal module, a glass or resin screen is installed on the front surface of the display device for the purpose of protecting the display device or improving design. However, since an air layer exists between the screen and the display device, there is a problem that it is difficult to see the display screen due to reflection of external light. Therefore, the air layer is bonded with a transparent adhesive that matches the refractive index of the screen. As an adhesive used therefor, an ultraviolet curable type is generally used. The adhesive is applied to one side of opposing members to be bonded, and the members are bonded together, and then cured with ultraviolet rays.

  In recent years, the use of plastic resin that is difficult to transmit ultraviolet rays to the screen material due to the variety of designs and the provision of frame printing with colored areas around the screen has increased the number of cases where ultraviolet rays do not transmit and are difficult to cure. It is coming. On the other hand, Patent Document 1 discloses that a compound having an average of at least one hydrolyzable silyl group in one molecule and an average of at least one polymerizable carbon-carbon double bond in one molecule. A curable composition containing the compound is disclosed. The composition described in Patent Document 1 is a curable composition that can be quickly cured by light and that is cured by reacting with moisture in the atmosphere even in a portion that is not exposed to light. Patent Document 2 discloses a two-component addition anti-silicone gel that cures by heating.

JP 2010-248347 A JP 2004-272059 A

  In the composition disclosed in Patent Document 1, since curing occurs in the coating apparatus, the problem of causing clogging of the coating apparatus and a long reaction time with moisture in the first place, the curing reaction after bonding is very slow. There was a problem.

  When the thermosetting composition disclosed in Patent Document 2 is interposed between the display device and the protective plate and thermally cured, there is a problem that the curing time is long and the protective plate is displaced. Although it is conceivable to cure the protective plate in a short time by applying a high temperature, there is a problem that sufficient heat cannot be applied for curing because of the heat resistance of the member to be bonded. .

  As described above, it is not necessary to use a special device such as radiation or a heating device in the curing reaction, and even a member that does not transmit ultraviolet rays or a member having poor heat resistance can be bonded, and it is not affected by the external environment such as moisture. Newly suitable for the bonding method in which the curing reaction is started when the adhesive components are contacted with each other by applying the adhesive to the substrates to be bonded to each other and bonding the substrates together. There is a growing need for new curable polyorganosiloxane compositions.

  An object of this invention is to provide the curable polyorganosiloxane composition excellent in quick-curing property.

The present invention
(A) an alkenyl group-containing polyorganosiloxane containing two or more alkenyl groups in the molecule;
(B) a polyorganohydrogensiloxane having two or more hydrogen atoms bonded to silicon atoms in the molecule;
(C) including a platinum-based catalyst,
The ratio of the number H _B of hydrogen atoms bonded to the silicon atom in (B) to the number Vi _A of alkenyl groups in (A) is 0.5 to 10,
(C) A component is 0.5-2000 ppm as a platinum-type metal atom,
A two-part curable polyorganosiloxane composition comprising a first component and a second component,
The first component comprises (A) and (C);
The second component comprises (B),
The present invention relates to a two-part curable polyorganosiloxane composition.

  ADVANTAGE OF THE INVENTION According to this invention, the curable polyorganosiloxane composition excellent in rapid curability is provided.

The (A) alkenyl group-containing polyorganosiloxane of the present invention is a component that becomes a base polymer in the polyorganosiloxane composition of the present invention. By blending (A), it is possible to ensure a stable three-dimensional structure by a crosslinking reaction during curing, to control and suppress curing shrinkage, and to ensure good visibility. (A) has two or more alkenyl groups bonded to a silicon atom in one molecule, and can form a network structure by addition reaction with the Si—H bond in (B), Any thing is acceptable. Typically, the general formula (I):
(R ^a ) _n1 (R ^b ) _n2 SiO _{(4-n1-n2) / 2} (I)
(Where
R ^a is a C ₂ -C ₆ alkenyl group (eg, vinyl, allyl, 3-butenyl, 5-hexenyl);
R ^b is a C ₁ -C ₆ alkyl group (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl) or phenyl;
n1 is 1 or 2;
n2 is an integer of 0 to 2, provided that n1 + n2 is 1 to 3)
Is an alkenyl group-containing polyorganosiloxane having at least two alkenyl group-containing siloxane units in the molecule.

  The siloxane skeleton of (A) may be linear or branched. Since the synthesis and control of the average degree of polymerization are easy, (A) is preferably a straight chain. Moreover, you may use these mixtures.

R ^a is preferably a vinyl group because it is easy to synthesize and does not impair the fluidity of the composition before curing and the heat resistance of the cured product. R ^a may be present at either the end or in the middle of the polyorganosiloxane molecular chain of (A), or may be present at both of them, in order to give excellent mechanical properties to the composition after curing. Is preferably present at least at both ends thereof.

^Rb is particularly preferably a methyl group because it is easy to synthesize and has an excellent balance of fluidity of the composition and mechanical strength after curing.

  n1 is preferably 1 because synthesis is easy.

  In (A), from the viewpoint of workability, the viscosity of (A) is preferably 100 to 100,000 cP, more preferably 100 to 10,000 cP, and particularly preferably 300 to 4,000 cP at 23 ° C. It is preferable to adjust the weight average molecular weight of (A) so as to be in these viscosity ranges. In addition, the viscosity in this invention is the value measured on the conditions of 23 degreeC using the rotational viscometer.

（式中、
Ｒ^ａは、独立して、Ｃ_２−Ｃ_６アルケニル基であり、
Ｒ^ｂは、独立して、Ｃ_１−Ｃ_６アルキル基又はフェニル基であり、
ｍ１は、（Ａ）の２３℃における粘度を１００〜１００，０００ｃＰにする数である）で示されるアルケニル基含有直鎖状ポリオルガノシロキサンが好ましい。 Therefore, as (A), the formula (Ia):

(Where
R ^a is independently a C ₂ -C ₆ alkenyl group,
R ^b is independently a C ₁ -C ₆ alkyl group or a phenyl group;
m1 is preferably an alkenyl group-containing linear polyorganosiloxane represented by (A) having a viscosity at 23 ° C. of 100 to 100,000 cP.

  Further, as (A), an alkenyl group in which both ends are blocked with dimethylvinylsiloxane units, an intermediate unit is polymethylvinylsiloxane composed of dimethylsiloxane units, and a viscosity at 23 ° C. is 100 to 100,000 cP. Containing linear polyorganosiloxane is more preferable.

The polyorganohydrogensiloxane (B) of the present invention functions as a crosslinking agent of (A) by the addition of ^a hydrosilyl group contained in the molecule with Ra of (A). is there. In order to reticulate the cured product, it has two or more hydrogen atoms bonded to silicon atoms involved in the addition reaction. Such polyorganohydrogensiloxane is typically represented by the general formula (II):
(R ^c ) _n3 (R ^d ) _n4 SiO _{(4-n3-n4) / 2} (II)
(Where
R ^c is a hydrogen atom,
R ^d is a C ₁ -C ₆ alkyl group or a phenyl group;
n3 is 1 or 2;
n4 is an integer of 0 to 2, provided that n3 + n4 is 1 to 3)
2 or more units in the molecule.

R ^d is exemplified by those similar to R ^b in (A) described above, including preferred ones. Further, n3 is preferably 1 because synthesis is easy.

  The siloxane skeleton in (B) may be linear, branched or cyclic. Moreover, you may use these mixtures.

  (B) preferably has a viscosity at 23 ° C. of 1 to 10,000 cP, more preferably 1 to 1,000 cP, still more preferably 1 to 200 cP, and more preferably 1 to 50 cP. Particularly preferred.

（式中、
Ｒ^ｃは、水素原子であり、
Ｒ^ｄは、独立して、Ｃ_１−Ｃ_６アルキル基又はフェニル基であり、
ｍ２は、（Ｂ３）の２３℃における粘度を１〜１０，０００ｃＰとする数である）で示される、直鎖状ポリオルガノハイドロジェンシロキサン
が好ましい。また、硬化性を高くするという観点から、（Ｂ１）がより好ましい。（Ｂ１）、（Ｂ２）及び（Ｂ３）は、単独で用いてもよく、組み合わせて用いてもよい。（Ｂ）として、（Ｂ１）及び（Ｂ３）の組合せ、（Ｂ１）、並びに（Ｂ２）がさらに好ましい。 As such (B), the following (B1), (B2) and (B3):
(B1) R ^e ₂ HSiO _1/2 unit wherein R ^e is a hydrogen atom or a C ₁ -C ₆ alkyl group (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl) and SiO _A cyclic polyorganohydrogensiloxane comprising _4/2 units and having two or more hydrogen atoms bonded to silicon atoms in one molecule;
(B2) Both ends are blocked with R ^d ₃ SiO _1/2 units, intermediate units are R ^c R ^d SiO _2/2 units and R ^d ₂ SiO _2/2 units (wherein R ^c is a hydrogen atom) R ^d is independently a C ₁ -C ₆ alkyl group or a phenyl group), and has a viscosity at 23 ° C. of 1 to 10,000 cP, a linear polyorganohydrogensiloxane; and ( B3) Formula (III):

(Where
R ^c is a hydrogen atom,
R ^d is independently a C ₁ -C ₆ alkyl group or a phenyl group;
m2 is preferably a linear polyorganohydrogensiloxane represented by (B3) having a viscosity of 1 to 10,000 cP at 23 ° C.). From the viewpoint of increasing curability, (B1) is more preferable. (B1), (B2) and (B3) may be used alone or in combination. (B) is more preferably a combination of (B1) and (B3), (B1), and (B2).

(B1) of the present invention is a cyclic polyorganohydrogensiloxane comprising R ^e ₂ HSiO _1/2 units and SiO _4/2 units, and having two or more hydrogen atoms bonded to silicon atoms in one molecule. is there. The number of hydrogen atoms in (B1) is preferably 3 to 100 and more preferably 3 to 50 in one molecule. R ^e as the C ₁ -C ₆ alkyl group is preferably methyl from the viewpoint of easiness of synthesis and the like.

As (B1), the ratio of R ^e ₂ HSiO _1/2 unit and SiO _4/2 unit is 1.5 to 2.2 mol of R ^e ₂ HSiO _1/2 unit with respect to 1 mol of SiO _4/2 unit. Is preferable, and 1.8 to 2.1 mol is more preferable. Typically, 3-5 SiO, such as [R ^e ₂ HSiO _1/2 ] ₈ [SiO _4/2 ] ₄ or [R ^e ₂ HSiO _1/2 ] ₁₀ [SiO _4/2 ] _{5 4/2} units form a cyclic siloxane skeleton, which each SiO _4/2 unit two ^R _e 2 _{HSiO 1/2} units combined is preferably, particularly preferably, the SiO _4/2 units Are bonded with _two (CH ₃ ) ₂ HSiO _1/2 units.

  The viscosity of (B1) is preferably 1 to 100 cP, and more preferably 1 to 50 cP.

(B2) of the present invention is a polyorgano in which both ends are blocked with R ^d ₃ SiO _1/2 units, intermediate units are R ^c R ^d SiO _2/2 units, and R ^d ₂ SiO _2/2 units. Hydrogen siloxane. R ^c in (B2) is preferably 2 to 5,000 in one molecule, more preferably 3 to 5,000, and still more preferably 20 to 1,000. R ^d in (B2) is preferably a methyl group from the viewpoints of easy synthesis and excellent balance of properties such as mechanical strength and fluidity before curing.

The _{^{(B2), R c R d}} SiO 2/2 units and the ratio of ^R _d 2 _{SiO 2/2} ^units, _R d _{2 SiO 2/2} units to 1 mole relative to ^R c ^R d _{SiO 2/2} units 0.1 to 2.0 mol is preferable, and 0.5 to 1.5 mol is more preferable. Therefore, as (B2), both ends are blocked with trimethylsiloxane units, the intermediate unit is composed of a dimethylsiloxane unit and a methylhydrogensiloxane unit, and 0.1 mol of methylhydrogensiloxane unit per 1 mol of dimethylsiloxane unit. To 2.0 mol of polymethylhydrogensiloxane is preferred.

  The viscosity of (B2) is preferably 1 to 10,000 cP, more preferably 1 to 1,000 cP.

  (B3) of the present invention is a linear polyorganohydrogensiloxane represented by the formula (III).

R ^d in (B3) is preferably a methyl group from the viewpoint of easy synthesis and excellent balance of properties such as mechanical strength and fluidity before curing.

  (B3) is preferably polymethylhydrogensiloxane in which both ends are blocked with dimethylhydrogensiloxane units and the intermediate unit is composed of dimethylsiloxane units.

  The viscosity of (B3) is preferably 1 to 5,000 cP at 23 ° C. From the viewpoint of impact resistance of the cured product, (B3) is preferably 10 to 1000 parts by weight and preferably 20 to 800 parts by weight with respect to a total of 100 parts by weight of (B1) and (B2). More preferred.

From the viewpoint of ensuring proper cure rate, the ratio of the total number Vi _A of alkenyl groups bonded to silicon atoms, the total number H _B of the hydrogen atoms bonded to silicon atoms in (B) of (A) ( H _B / Vi _A ) is 0.5 to 10, preferably 1.0 to 6.0.

  (C) of the present invention is a catalyst for promoting the addition reaction between the alkenyl group of (A) and the Si—H group of (B). From the viewpoint of good catalytic activity, platinum group metal atom compounds such as platinum, rhodium and palladium are preferably used. Chloroplatinic acid, reaction product of chloroplatinic acid and alcohol, platinum-olefin complex, platinum-vinyl Platinum compounds such as siloxane complexes, platinum-ketone complexes, platinum-phosphine complexes, rhodium-phosphine complexes, rhodium compounds such as rhodium-sulfide complexes, palladium compounds such as palladium-phosphine complexes are preferred, and platinum compounds are more preferred. More preferred are platinum-vinylsiloxane complexes.

  (C) is from 0.5 to 2000 ppm, preferably from 1 to 500 ppm by weight, more preferably from 5 to 200 ppm by weight, more preferably from the viewpoint of ensuring an appropriate curing rate. 20 to 100 ppm by weight. Moreover, from a viewpoint of ensuring the transparency of hardened | cured material, Preferably it is 5-200 weight ppm in conversion of a platinum group metal atom, More preferably, it is 20-100 weight ppm, More preferably, it is 20-50 weight ppm.

  The composition of the present invention contains (D) a stabilizer having a nitrogen atom, (E) a diluent, (F) an adhesion-imparting agent, (G) an inorganic filler, and the like within a range not impairing the effects of the present invention. May be.

The composition of the present invention may contain (D) a stabilizer having a nitrogen atom. (D) can stabilize (C) the platinum-based catalyst. (D) is, for example, a general formula: (R ¹ ) ₂ N—R ³ —N (R ² ) ₂ (wherein R ¹ independently represents a C ₁ -C ₆ alkyl group (for example, Methyl, ethyl, propyl, butyl, pentyl, hexyl), R ² has the same meaning as R ¹ , or is a hydrogen atom, and R ³ is a C ₂ -C ₄ alkylene group (eg, ethylene, And an amine compound represented by the following formula:

  As (D), specifically, N, N, N ′, N′-tetramethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, N, N-dibutyl -1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N, N ′, N′-tetraethylethylenediamine, N, N-dibutyl-1,4-butanediamine, N, N, N ′, N′-tetramethylethylenediamine is preferred. (D) can be used individually or in mixture of 2 or more types.

  The blending amount of (D) is in the range of 0.001 to 0.5 mol, preferably 0.01 to 0.1 mol, with respect to 1 mol of the platinum group metal atom of (C). Within such a range, the appearance of the resulting catalyst can be prevented from poor appearance over time, discoloration can be suppressed, and curing in a desired time can be achieved without extremely reducing the catalytic activity of the platinum catalyst.

  The composition of the present invention may contain (E) a diluent for the purpose of adjusting the viscosity. (E) is a silicone oil that does not contain an alkenyl group or a hydrosilyl group involved in the effect reaction of the present invention, and polymethylsiloxane having both ends blocked with trimethylsiloxane units and an intermediate unit consisting of dimethylsiloxane units is preferred. (E) preferably has a viscosity of 1 to 1,000 cP, more preferably 5 to 300 cP. The blending amount of (E) is preferably 50% by weight or less of each component (first component and second component) in the two-component curable polyorganosiloxane composition of the present invention, and is 30% by weight or less. More preferably, it is more preferably 20% by weight or less.

  The composition of the present invention may contain (F) an adhesion-imparting agent. (F) Examples of the adhesion-imparting agent include alkoxysilanes, for example, reaction products of 1,1,3,5,7-pentamethylcyclotetrasiloxane and 3-methacryloxypropyltrimethoxysilane.

（式中、Ｑ¹およびＱ²は、互いに独立して、アルキレン基、好ましくはＣ_１−Ｃ_４アルキレン基を表し、Ｒ³は、Ｃ_１−Ｃ_４アルキル基を表す）で示される側鎖を有するアルコキシシラン類が好ましい。 Specifically, the following formula:

(Wherein Q ¹ and Q ² each independently represent an alkylene group, preferably a C ₁ -C ₄ alkylene group, and R ³ represents a C ₁ -C ₄ alkyl group). Alkoxysilanes having are preferred.

Examples of such alkoxysilanes include the following compounds.

  Examples of the inorganic filler (G) include dry fine powder silica such as fumed silica and arc silica, and fumed silica is preferable. In addition, such a silica surface is treated with a silazane compound such as hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane; a polyorganosiloxane such as octamethylcyclotetrasiloxane. Etc. may be processed.

  The curable polyorganosiloxane composition of the present invention is a two-part curable polyorganosiloxane composition comprising a first component and a second component, wherein the first component comprises (A) and (C). The second component includes the component (B). The first component does not include (B), and the second component does not include (C). In this invention, each component contained in a 1st component and a 2nd component contacts only at the time of bonding, and a crosslinking reaction advances. Therefore, the room temperature curable polyorganosiloxane composition of the present invention has excellent storage stability.

The first component preferably further contains (D) from the viewpoint of stabilizing the component (C). Moreover, it is more preferable that the first component further includes (D) and (E).
The first component of the present invention preferably has a viscosity at 23 ° C. of 100 to 100,000 cP, more preferably 100 to 10,000 cP, and particularly preferably 300 to 4,000 cP. In such a range, workability is improved, spreadability at the time of application is good, each component contained in the first component and the second component is easily mixed at the time of bonding, the reactivity is improved, and curing is performed. Time is further reduced. Further, in the addition reaction between (A) and (B), a large cross-linked structure is formed at a small number of reaction points, which further shortens the curing time. It is preferable that a component having a large organosiloxane molecular chain, that is, a component (A) having a high viscosity is present. From the viewpoint of obtaining such a first component, the first component has a high viscosity as (A) (for example, a viscosity at 23 ° C. of 30,000 to 100,000 cP) and a low viscosity (for example, Polysiloxane containing a mixture of polyorganosiloxane having a viscosity at 23 ° C. of 50 to 1,000 cP) or having a high viscosity as the first component (A) (for example, a viscosity at 23 ° C. of 30,000 to 100,000 cP) Preferably, methyl vinyl siloxane and (E) diluent are included. In the mixture of a polyorganosiloxane having a high viscosity and a polyorganosiloxane having a low viscosity, the amount of the polyorganosiloxane having a low viscosity is not particularly limited as long as the above viscosity is satisfied. For example, 30 parts by weight of a polyorganosiloxane having a high viscosity In contrast, it can be 30 to 60 parts by weight.

The second component preferably further includes (A), and more preferably includes (A) and (E). For the uniformity of the resulting cured product, (A) and (E) contained in the first component are preferably the same as (A) and (E) contained in the second component.
In the present invention, when (A) is contained in the second component, the content ratio of (A) contained in the first component and the second component is particularly limited as long as the H _B / Vi _A ratio of the present invention is satisfied. Not. For example, with respect to 100 parts by weight of the first component (A), the amount of the second component (A) can be 50 to 200 parts by weight, and preferably 80 to 120 parts by weight.

  The second component of the present invention preferably has a viscosity at 23 ° C. of 100 to 100,000 cP, more preferably 100 to 10,000 cP, and particularly preferably 300 to 4,000 cP. In such a range, workability is improved, spreadability at the time of application is good, each component contained in the first component and the second component is easily mixed at the time of bonding, the reactivity is improved, and curing is performed. Time is further reduced. In addition, in the addition reaction between (A) and (B), a large cross-linked structure is formed at a small number of reaction points, which further shortens the curing time. It is preferable that a component having a large organosiloxane molecular chain, that is, a component (A) having a high viscosity is present. From the viewpoint of obtaining such a second component, the second component has a high viscosity as (B) and (A) (for example, the viscosity at 23 ° C. is 30,000 to 100,000 cP) and the viscosity of the polyorganosiloxane. It contains a mixture of polyorganosiloxanes that are low (for example, the viscosity at 23 ° C. is 50 to 1,000 cP), or the second component is high as (B) and (A) (for example, the viscosity at 23 ° C. is 30 , 1,000 to 100,000 cP) polymethylvinylsiloxane, and (E) a diluent. Here, in the mixture of the polyorganosiloxane having a high viscosity and the polyorganosiloxane having a low viscosity, the amount of the polyorganosiloxane having a low viscosity is not particularly limited as long as the above viscosity is satisfied. It can be 30-60 weight part with respect to 30 weight part.

  The first component of the present invention can be prepared by uniformly kneading (A), (C), and other components blended as necessary, by a mixing means such as a universal kneader or a kneader. Moreover, a 2nd component can be prepared like the 1st component using (B) and the other component mix | blended as needed further.

  The composition of the present invention is cured at room temperature (for example, 20 to 25 ° C.) after the first component and the second component are in contact with each other, and exhibits an adhesive force. That is, the composition of the present invention is cured only when the first component and the second component are stored as they are in different containers and brought into contact with each other during use. The composition of the present invention is cured in 0.1 to 10 minutes after the first component and the second component are in contact with each other, and exhibits an adhesive force. The curing time is preferably from 0.1 to 8 minutes, and more preferably from 0.1 to 6 minutes. Moreover, the composition of this invention may heat at the temperature of 50-80 degreeC depending on the case after said hardening, may accelerate | stimulate hardening more, and may raise adhesive force more. Although heating time can be set suitably, it can be 0.1 to 3 hours, for example.

  The composition of the present invention can have a transmittance after curing of 70 to 100%, preferably 80 to 100%, more preferably 90 to 100%. Since it has good transmittance, it is also good in terms of visibility after the composition is cured between the base portion having the image display portion of the image display device and the translucent protective portion.

  The composition of the present invention can be used as an adhesive for bonding various substrates. Specifically, the two-component curable polyorganosiloxane composition of the present invention is an adhesive for bonding two substrates, and the first component is applied to the adherend surface of one substrate. Pasting two substrates, including a step of applying, a step of applying the second component to the adherend surface of the substrate not coated with the first component, and a step of bonding and curing and bonding the applied substrate. It can be used as an adhesive for matching. The composition of the present invention is preferably an adhesive for bonding a base portion of an image display portion of an image display device such as a cathode ray tube, liquid crystal, plasma, organic EL or the like and a translucent protective portion.

  The manufacturing method of the adhesive body containing two base materials using the two component type curable polyorganosiloxane composition which consists of the 1st component and 2nd component of this invention is the 1st base material on the to-be-adhered surface. It includes a step of applying one component, a step of applying the second component to the adherend surface of the base material to which the first component is not applied, and a step of bonding and curing and bonding the applied base material.

  Base materials include metals such as aluminum, iron, zinc, copper, magnesium alloys, epoxy resins, acrylic resins, plastics such as ABS, PA, PBT, PC, PPS, SPS, and glass, cathode ray tubes, liquid crystals, plasma The base of the image display unit of the image display device such as organic EL and the light-transmitting protective unit are preferable.

  Although the usage-amount of the 1st component or 2nd component apply | coated to a base material is not specifically limited, For example, a 2nd component is 10-200 weight part with respect to 100 weight part of 1st components. Preferably, 90-1200 weight part is more preferable.

  The coating thickness of the first component or the second component is not particularly limited, but is preferably 10 to 1,000 μm, and more preferably 100 to 500 μm.

  The application method to the substrate is not particularly limited as long as it can be applied accurately to the position of the target surface to be bonded and the entire adhesive body can be filled with an adhesive, and examples include a method using a dispenser and a slot die coater. It is done.

  The bonding method is not particularly limited, and examples thereof include a method of bonding under vacuum and a method of bonding under atmospheric pressure.

  In the present invention, a step of heating at a temperature of 50 to 80 ° C. may optionally be included after the step of bonding, curing and adhering the coated base material. Thereby, hardening is accelerated | stimulated more and adhesive force becomes higher.

  An adhesive (for example, reactive) having a composition different from the curable polyorganosiloxane composition of the present invention using the curable polyorganosiloxane composition of the present invention as a part of the adherend surface. Adhesives may be produced using a low one-component polyorganosiloxane composition), but from the viewpoint of uniformity of properties such as optical properties and adhesiveness of the resulting cured product, (A) and (B) contained in an adhesive which is a composition different from the composition of (A) and (B) contained in the curable polyorganosiloxane composition of the present invention and the curable polyorganosiloxane composition of the present invention. ) Are preferably the same.

  Therefore, the manufacturing method of the adhesive body containing two base materials which is a preferable embodiment of the present invention is an image using a two-component curable polyorganosiloxane composition comprising the first component or the second component of the present invention. A method for manufacturing an image display device including a base portion of a display device and a translucent protective portion, the step of applying a first component or a second component to the adherend surface of the base portion of the image display portion of the image display device, Applying the second component or the first component (but different from the component applied to the adherend surface of the base of the image display portion of the image display device) to the adherend surface of the translucent protection portion; A step of bonding the base portion of the image display portion of the image display device and the translucent protective portion together and curing and bonding them. In addition, you may provide the level | step difference for preventing the outflow of a composition in an outer peripheral edge part as needed in the base of an image display part.

  Specifically, as an image display device obtained by the method of manufacturing an adhesive body comprising the composition of the present invention and the two substrates using the composition of the present invention, the image display device is large (50 to 100 inches). Examples thereof include a plasma panel display and a mobile phone having a small image display device (less than 1 to 50 inches). Further, these image display devices may include a touch sensor.

Next, the present invention will be described in more detail with reference to Examples , Reference Examples and Comparative Examples. However, the present invention is not limited to these examples. In the compositions shown in Tables 1 to 3, the respective components were kneaded by hand mixing to prepare a two-component composition comprising the first component and the second component of Examples , Reference Examples and Comparative Examples.

Each component used is as follows.
A1: Polymethylvinylsiloxane having both ends blocked with dimethylvinylsiloxane units and intermediate units consisting of dimethylsiloxane units (viscosity at 23 ° C., 82,000 cP)
A2: Polymethylvinylsiloxane in which both ends are blocked with dimethylvinylsiloxane units and the intermediate units are dimethylsiloxane units (viscosity at 23 ° C .: 420 cP)
A3: Polymethylvinylsiloxane having both ends blocked with dimethylvinylsiloxane units and intermediate units consisting of dimethylsiloxane units (viscosity at 23 ° C. of 110 cP)
B1: The average unit formula is [H (CH ₃ ) ₂ SiO _1/2 ] ₈ [SiO _4/2 ] ₄ (hydrogen amount: 1.05% by weight)
B2: Polymethylhydrogensiloxane having both ends blocked with trimethylsiloxane units and intermediate units composed of dimethylsiloxane units and methylhydrogensiloxane units (structural formula: [(CH ₃ ) ₃ SiO _1/2 ] [H (CH ₃ ) SiO _2/2 ] ₅₅ [(CH ₃ ) ₂ SiO _2/2 ] ₅₅ [(CH ₃ ) ₃ SiO _1/2 ], viscosity at 23 ° C. 100 cP)
B3: Polymethylhydrogensiloxane having both ends blocked with dimethylhydrogensiloxane units and an intermediate unit consisting of dimethylsiloxane units (viscosity at 23 ° C., 20 cP)
C: a complex obtained by heating chloroplatinic acid to 1,3-divinyl-1,1,3,3-tetramethyldisiloxane at a molar ratio of 1: 4 and having a platinum content of 4.91% by weight .
D: N, N, N ′, N′-tetramethylethylenediamine E: Polymethylsiloxane having both ends blocked with trimethylsiloxane units and intermediate units consisting of dimethylsiloxane units (viscosity at 23 ° C. 100 cP)

The physical properties were evaluated as follows. The results are shown in Tables 1 to 3.
(1) Viscosity Viscosity at 23 ° C. was measured using a rotational viscometer (Bismetron VDA-L) (manufactured by Shibaura System Co., Ltd.).

(2) Temporary fixing time The first component is placed in the center of the first glass plate (5 cm × 5 cm × 5 mm thickness) so that the composition has a diameter of 2 cm and a thickness of 200 μm when the two glass plates are bonded together. An amount of 2 cm in diameter and a thickness of 100 μm was applied, and the second component was applied in the center of the second glass plate (7.6 cm × 7.6 cm × 1 mm thickness) in an amount of 2 cm in diameter and a thickness of 100 μm. At room temperature (25 ° C.), the second glass is laminated on the first glass, tilted 90 degrees every 15 seconds, and stands vertically to measure the time until the first glass does not shift due to weight. It was.

(3) Yellow Index The amount of the first component is 2 cm in diameter and 100 μm in the center of the first glass plate (5 cm × 5 cm × 5 mm thick) so that the compositions of Examples , Reference Examples and Comparative Examples are 200 μm thick. The second component was applied in the center of the second glass plate (7.6 cm × 7.6 cm × 1 mm thickness) in an amount of 2 cm in diameter and 100 μm in thickness. At room temperature (25 ° C.), the second glass was laminated on the first glass, and after the sample cured for 30 minutes at room temperature and 30 minutes at 70 ° C. was returned to the state of 23 ° C., the index of the degree of discoloration A certain yellow index was evaluated by a spectrophotometer (CM-3500d manufactured by Minolta Co., Ltd.).

(4) Transmittance The amount of the first component in the center of the first glass plate (5 cm × 5 cm × 5 mm thickness) is 2 cm in diameter and 100 μm thick so that the compositions of Examples , Reference Examples and Comparative Examples are 200 μm thick. The second component was applied in the center of the second glass plate (7.6 cm × 7.6 cm × 1 mm thickness) in an amount of 2 cm in diameter and 100 μm in thickness. At room temperature (25 ° C.), the second glass was bonded onto the first glass, and after the sample cured for 30 minutes at room temperature and 30 minutes at 70 ° C. was returned to 23 ° C., the degree of transparency was increased. The transmittance as an index was evaluated by a spectrophotometer (CM-3500d manufactured by Minolta Co., Ltd.).

The two-component compositions of Examples and Reference Examples all exhibited excellent quick curability and adhesiveness. From these, the composition of the present invention does not require the use of a special device such as radiation or a heating device in the curing reaction, and can be bonded even with a member that does not transmit ultraviolet rays or a member with poor heat resistance, and with an external environment such as moisture. It can be seen that the curing reaction is possible without being affected by the above. On the other hand, the two-component composition of the comparative example did not exhibit curability and adhesiveness even after 30 minutes.

  The two-part curable polyorganosiloxane composition of the present invention is used for adhesion of various substrates, in particular, a base having an image display part of an image display device such as a cathode ray tube, liquid crystal, plasma, organic EL, and a translucent protective part. It is useful for adhesion to

Claims (7)

(A) an alkenyl group-containing polyorganosiloxane containing two or more alkenyl groups in the molecule;
(B) a polyorganohydrogensiloxane having two or more hydrogen atoms bonded to silicon atoms in the molecule; and (C) a platinum-based catalyst,
The ratio of the number H _B of hydrogen atoms bonded to the silicon atom in (B) to the number Vi _A of alkenyl groups in (A) is 0.5 to 10.0,
(C) is 5 to 200 ppm as a platinum-based metal atom,
A two-part curable polyorganosiloxane composition comprising a first component and a second component,
The first component comprises (A) and (C);
The second component comprises (B),
The step of applying the first component to the adherend surface of one substrate, the step of applying the second component to the adherend surface of the substrate not coated with the first component, and bonding the coated substrate together A two-part curable polyorganosiloxane composition, which is an adhesive for bonding two substrates together, including a step of curing and bonding. (A) is represented by formula (Ia):

(Where
R ^a is independently a C ₂ -C ₆ alkenyl group,
R ^b is independently a C ₁ -C ₆ alkyl group or a phenyl group;
The two-part curable polyorganosiloxane composition according to claim 1, wherein m1 is an alkenyl group-containing linear polyorganosiloxane having a viscosity at 23 ° C of 100 to 100,000 cP). . (B)
(B1) R ^e ₂ HSiO _1/2 unit (wherein R ^e represents a hydrogen atom or a C ₁ -C ₆ alkyl group) and a SiO _4/2 unit, and bonded to a silicon atom in one molecule A cyclic polyorganohydrogensiloxane having two or more hydrogen atoms;
(B2) Both ends are blocked with R ^d ₃ SiO _1/2 units, intermediate units are R ^c R ^d SiO _2/2 units and R ^d ₂ SiO _2/2 units (wherein R ^c is a hydrogen atom) R ^d is independently a C ₁ -C ₆ alkyl group or a phenyl group), and has a viscosity at 23 ° C. of 1 to 10,000 cP, a linear polyorganohydrogensiloxane; and ( B3) Formula (III):

(Where
R ^c is a hydrogen atom,
R ^d is independently a C ₁ -C ₆ alkyl group or a phenyl group;
m2 is a linear polyorganohydrogensiloxane represented by (B3) having a viscosity at 23 ° C. of 1 to 10,000 cP),
The two-part curable polyorganosiloxane composition according to claim 1 or 2, which is at least one polyorganohydrogensiloxane selected from the group consisting of:   The two-component type according to any one of claims 1 to 3, wherein the viscosity of the first component is 100 to 100,000 cP at 23 ° C, and the viscosity of the second component is 100 to 100,000 cP at 23 ° C. A curable polyorganosiloxane composition.   The two-component curable polyorganosiloxane composition according to any one of claims 1 to 4, which is an adhesive between a base having an image display part of an image display device and a translucent protective part.   It is a manufacturing method of the adhesive body containing two base materials using the two agent type curable polyorganosiloxane composition of any one of Claims 1-4, Comprising: The to-be-adhered surface of one base material The step of applying the first component to the substrate, the step of applying the second component to the adherend surface of the substrate to which the first component has not been applied, and the step of bonding and curing and bonding the applied substrate. Production method.   An image display in which a base having an image display portion of an image display device and a translucent protective portion are bonded using the two-part curable polyorganosiloxane composition according to any one of claims 1 to 5. A method for manufacturing an apparatus, the step of applying a first component or a second component to a bonded surface of a base portion of an image display unit of an image display device, a second component or a second component applied to a bonded surface of a translucent protection unit. A step of applying one component (however, different from the component applied to the adherend surface of the base of the image display unit of the image display device), and the base of the image display unit of the applied image display device and the translucent protection The manufacturing method of an image display apparatus including the process of bonding and hardening | curing and bonding a part.