JP2019108471A - Ultraviolet curable resin composition, adhesive and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To hardly inhibit photoactivation of a platinum catalyst even if it contains a polymer having an organic skeleton absorbing ultraviolet rays, to be able to cure under mild conditions using ultraviolet rays, and to have excellent hardness and a base material. Provided is an ultraviolet curable resin composition that gives a cured product exhibiting adhesiveness to and from. A polymer represented by the formula (1) (A): [X is a phenylene group, Y is a monovalent group having a specific structure having a vinyl norbornane structure or a norbornene structure, and Y'is a specific group having a norbornane structure. The divalent group of the structure, Me is a methyl group, and m is an integer of 0 to 12. ] (B) An organosilicon compound having at least two SiH groups in one molecule, and (C) a platinum group metal catalyst activated by light having a wavelength of 200 to 500 nm, an ultraviolet curable resin composition. [Selection diagram] None

Description

  The present invention relates to an ultraviolet curable resin composition useful as a material for an optical device or an optical component, an insulating material for an electronic device or an electronic component, a coating material, etc., an adhesive comprising the ultraviolet curable resin composition, the ultraviolet curable resin composition The present invention relates to a cured product of a resin composition and a method for producing the same.

  Organic modified silicone resins such as alkylene modified silicone resin and arylene modified silicone resin have high heat resistance and high transparency possessed by silicone resin (dimethyl silicone resin), and high possessed by organic resin such as polyolefin resin and polyethylene terephthalate resin It is a hybrid resin that has both the properties of hardness, high toughness, and high gas barrier properties. Therefore, they are used in electrical and electronic applications such as light emitting devices and sensors that require sealing and coating, and are drawing high attention from other fields.

However, on the other hand, it has often been a problem that the curing conditions for fully curing the solution require 3 hours or more at 150 ° C. That is, after being cured at a high temperature, the resin may be cracked or peeled from the substrate by being allowed to cool at normal temperature or the like.
In addition, since the viscosity of the liquid agent is lowered by heating, a phenomenon in which the liquid agent crawls to an unintended site, and a phenomenon in which solid additives such as phosphors are sometimes precipitated.
Furthermore, when curing is performed in the open state in air in a heating furnace, the silicone layer at the interface with the gas phase cures slightly faster than the silicone layer in the liquid phase, so wrinkles occur on the surface of the cured product. It happened.
In addition to these technical problems, problems related to mass productivity such as deterioration of production efficiency and increase in cost have sometimes become problems.

  On the other hand, in recent years, a UV addition-curable silicone resin composition has been proposed. Although this material activates the platinum catalyst by irradiating ultraviolet light to promote the curing of the material, it is known that the curing proceeds rapidly even under relatively mild curing conditions. That is, it is possible to obtain a resin having sufficient hardness and strength by irradiating a liquid agent with an appropriate amount of ultraviolet light and leaving it to stand under a mild temperature condition of about room temperature to 100 ° C.

However, an effective ultraviolet wavelength range for activating a platinum catalyst is 200 to 500 nm, and in this wavelength range, no extreme absorption or attenuation occurs in the case of dimethyl silicone resin, but in the case of an organic modified silicone resin Ultraviolet light can be absorbed by the organic sites in it. If this UV absorption is large, the platinum catalyst is hard to be photoactivated, so curing is considered to be delayed, or curing does not occur at all, so it was necessary to select a framework with low UV absorption.
As prior art documents related to the present invention, the following can be mentioned.

JP 2005-133073 A JP, 2010-47646, A

  The present invention has been made in view of the above-mentioned circumstances, and the photoactivation of a platinum catalyst is difficult to be inhibited even if it contains a polymer having an ultraviolet-absorbing organic skeleton, under mild conditions using ultraviolet light. UV curable resin composition capable of curing of the above, giving a cured product exhibiting excellent hardness and adhesiveness with a substrate, an adhesive comprising the composition, a cured product of the above composition and a method for producing the same The purpose is

  As a result of intensive studies to solve the above problems, the present inventors are able to cure resin compositions containing the following components (A) to (C) under mild conditions using ultraviolet light, The present invention has been completed by finding that it provides a cured product exhibiting excellent hardness and adhesion to a substrate.

［式中、Ｘはそれぞれ独立に下記構造式（２）で表される２価の基であり、Ｙはそれぞれ独立に下記構造式（３）〜（５）のいずれかで表される１価の基であり、Ｙ’はそれぞれ独立に下記構造式（６）または（７）で表される２価の基であり、Ｍｅはメチル基を表す。ｍは０〜１２の整数である。

（式中、アスタリスク（＊）はケイ素原子との結合部位を示す。）

（式（３）〜（７）中、アスタリスク（＊）はケイ素原子との結合部位を示し、各不斉炭素における立体配置はシス（エキソ）またはトランス（エンド）のいずれであってもよい。）］
（Ｂ）１分子中に少なくとも２個のケイ素原子に結合した水素原子を有し、（メタ）アクリル基、カルボニル基、エポキシ基、アルコキシシリル基およびアミド基から選ばれる基を有しない有機ケイ素化合物、
（Ｃ）波長２００〜５００ｎｍの光によって活性化される白金族金属触媒
を含有する紫外線硬化型樹脂組成物、
２． 前記（Ｃ）成分が、（η⁵−シクロペンタジエニル）三脂肪族白金化合物またはビス（β−ジケトナト）白金化合物である１に記載の紫外線硬化型樹脂組成物、
３． （Ｂ）成分が、下記（ｉ）〜（ｉｉｉ）から選ばれる少なくとも１種である１または２に記載の紫外線硬化型樹脂組成物、
（ｉ）下記平均組成式（１０）で表されるオルガノハイドロジェンポリシロキサン：
Ｒ¹ _aＨ_bＳｉＯ_[(4-a-b)/2] （１０）
（式中、Ｒ¹はそれぞれ独立にアルケニル基以外の非置換もしくは置換の炭素原子数１〜１２の一価炭化水素基であり、ａ、ｂは０．７≦ａ≦２．１、０．０１≦ｂ≦１、かつ０．８≦ａ＋ｂ≦２．７を満たす数である。）
（ｉｉ）ビニルノルボルネンおよび／またはジアリルビスフェノールＡと環状オルガノハイドロジェンポリシロキサンとから得られるＳｉＨ基含有付加反応生成物
（ｉｉｉ）ＳｉＨ基含有シラン化合物
４． （ｉｉ）成分が、下記式（１１）または（１２）で示されるものである３に記載の紫外線硬化型樹脂組成物、

［式中、Ｚは前記Ｙで表される基または下記構造式（１３）で表される基であり、Ｚ’は前記Ｙ’で表される基または下記構造式（１４）で表される基であり、Ｍｅはメチル基を示す。ｓは０〜１００、好ましくは１〜１０の整数であり、ｔは１〜１００、好ましくは１〜２０の整数であり、ｑおよびｒはそれぞれ独立に０〜３の整数であり、それぞれの環状シロキサン部位におけるｑとｒの合計は独立に２または３である。

（式中、アスタリスク（＊）はケイ素原子との結合部位を示す。）

（式中、アスタリスク（＊）はケイ素原子との結合部位を示す。）］
５． （ｉｉｉ）成分が、下記式で示される化合物から選ばれる３または４に記載の紫外線硬化型樹脂組成物、

（式中、Ｍｅはメチル基、Ｐｈはフェニル基を示す。）
６． 更に、（Ｅ）１分子中に１個以上の（メタ）アクリル基、カルボニル基、エポキシ基、アルコキシシリル基およびアミド基から選ばれる少なくとも１個の基を含む接着助剤を含有する１〜５のいずれかに記載の紫外線硬化型樹脂組成物、
７． １〜６のいずれかに記載の紫外線硬化型樹脂組成物からなる接着剤、
８． １〜６のいずれかに記載の紫外線硬化型樹脂組成物の硬化物、
９． １〜６のいずれかに記載の紫外線硬化型樹脂組成物に紫外線を照射した後、６０〜１５０℃で加熱して硬化させる硬化物の製造方法
を提供する。 That is, the present invention
1. (A) Polymer Represented by the Following Structural Formula (1):

[Wherein, X is each independently a divalent group represented by the following structural formula (2), and Y is each independently a monovalent represented by any of the following structural formulas (3) to (5) And Y ′ each independently represents a divalent group represented by the following structural formula (6) or (7), and Me represents a methyl group. m is an integer of 0-12.

(In the formula, the asterisk (*) indicates a bonding site to a silicon atom.)

(In the formulas (3) to (7), the asterisk (*) represents a bonding site to a silicon atom, and the configuration at each asymmetric carbon may be either cis (exo) or trans (endo). )]
(B) Organosilicon compounds having hydrogen atoms bonded to at least two silicon atoms in one molecule and having no group selected from (meth) acrylic group, carbonyl group, epoxy group, alkoxysilyl group and amide group ,
(C) UV curable resin composition containing a platinum group metal catalyst activated by light having a wavelength of 200 to 500 nm,
2. The ultraviolet curable resin composition according to 1, wherein the component (C) is a (η ⁵ -cyclopentadienyl) trialiphatic platinum compound or a bis (β-diketonato) platinum compound,
3. The ultraviolet curable resin composition as described in 1 or 2 whose component (B) is at least one selected from the following (i) to (iii):
(I) Organohydrogenpolysiloxane represented by the following average composition formula (10):
R ¹ _a H _b SiO _{[(4-ab) / 2]} (10)
(Wherein, R ¹ is each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than an alkenyl group, and a and b each satisfy 0.7 ≦ a ≦ 2.1, 0. 01 ≦ b ≦ 1, and 0.8 ≦ a + b ≦ 2.7.
(Ii) SiH group-containing addition reaction product obtained from vinyl norbornene and / or diallyl bisphenol A and cyclic organohydrogenpolysiloxane (iii) SiH group-containing silane compound (Ii) The ultraviolet curable resin composition according to 3, wherein the component is represented by the following formula (11) or (12):

[Wherein, Z is a group represented by the above Y or a group represented by the following structural formula (13), and Z ′ is a group represented by the above Y ′ or represented by the following structural formula (14) And Me represents a methyl group. s is an integer of 0 to 100, preferably 1 to 10, t is an integer of 1 to 100, preferably 1 to 20, q and r are each independently an integer of 0 to 3, and each cyclic The sum of q and r at the siloxane site is independently 2 or 3.

(In the formula, the asterisk (*) indicates a bonding site to a silicon atom.)

(In the formula, the asterisk (*) represents a bonding site to a silicon atom.)]
5. (Iii) The ultraviolet curable resin composition according to 3 or 4, wherein the component is selected from compounds represented by the following formulae:

(Wherein, Me represents a methyl group and Ph represents a phenyl group)
6. Furthermore, (E) containing an adhesion promoter containing at least one group selected from one or more of (meth) acrylic group, carbonyl group, epoxy group, alkoxysilyl group and amide group in one molecule. UV curable resin composition according to any of
7. An adhesive comprising the ultraviolet curable resin composition according to any one of 1 to 6,
8. A cured product of the ultraviolet curable resin composition according to any one of 1 to 6,
9. The manufacturing method of the hardened | cured material which heats and hardens at 60-150 degreeC after irradiating an ultraviolet-ray to the ultraviolet curable resin composition in any one of 1-6 is provided.

  According to the present invention, since it is possible to obtain an organic modified resin cured product having sufficient hardness and adhesiveness to a substrate in a short time, it is possible to solve the technical or production problems of conventional materials. . In addition, since curing can proceed at a relatively low temperature, it can be applied to a substrate having low heat resistance. Therefore, the ultraviolet ray curable resin composition of the present invention is useful as a material for optical devices or optical parts, an insulating material for electronic devices or electronic parts, a coating material, an adhesive and the like.

Hereinafter, the present invention will be described in detail.

［式中、Ｘはそれぞれ独立に下記構造式（２）で表される２価の基であり、Ｙはそれぞれ独立に下記構造式（３）〜（５）のいずれかで表される１価の基であり、Ｙ’はそれぞれ独立に下記構造式（６）または（７）で表される２価の基であり、Ｍｅはメチル基を表す。ｍは０〜１２の整数である。

（式中、アスタリスク（＊）はケイ素原子との結合部位を示す。）

（式（３）〜（７）中、アスタリスク（＊）はケイ素原子との結合部位を示し、各不斉炭素における立体配置はシス（エキソ）またはトランス（エンド）のいずれであってもよい。）］
但し、前記構造式（６）または（７）で表される２価の基は、その結合方向が前記記載のとおりに限定されるものではなく、個々の構造を紙面上で１８０°回転させた構造をも包含する。 [A component]
The component (A) in the ultraviolet ray curable resin composition of the present invention is a polymer represented by the following structural formula (1).

[Wherein, X is each independently a divalent group represented by the following structural formula (2), and Y is each independently a monovalent represented by any of the following structural formulas (3) to (5) And Y ′ each independently represents a divalent group represented by the following structural formula (6) or (7), and Me represents a methyl group. m is an integer of 0-12.

(In the formula, the asterisk (*) indicates a bonding site to a silicon atom.)

(In the formulas (3) to (7), the asterisk (*) represents a bonding site to a silicon atom, and the configuration at each asymmetric carbon may be either cis (exo) or trans (endo). )]
However, the bonding direction of the divalent group represented by the structural formula (6) or (7) is not limited as described above, and each structure is rotated by 180 ° in the drawing. It also includes the structure.

  M in said Structural formula (1) is an integer of 0-12, Preferably it is 1-5. When m exceeds 12, the viscosity becomes high and handling becomes difficult.

Viscosity of component (A) is not particularly limited, is preferably from 1,000~100,000mm ² / s, more preferably 5,000~30,000mm ² / s. In the present invention, the viscosity is the value of the kinematic viscosity at 23 ° C. measured by a Canon Fence GmbH viscometer (the same applies hereinafter).

  Component (A) may be prepared, for example, as an addition reaction product of (a): bis (dimethylhydrosilyl) benzene and (b): vinyl norbornene according to a known method (Japanese Patent Laid-Open No. 2005-133073 etc.) it can.

The component (a) is an ortho-, meta- or para-substituted bis (dimethylhydrosilyl) benzene represented by the following structural formula (8), and two or more isomers can be used even if one having a single structure is used. You may use the mixture of. In the formula (8), Me represents a methyl group.

The component (b) is 5-vinylbicyclo [2.2.1] hept-2-ene or 6-vinylbicyclo [2.2.1] hept-2-ene represented by the following structural formula (9) There may be used a single structure or a mixture of two or more isomers.

  The component (A) of the present invention has, for example, two addition-reactive carbon-carbon double bonds in one molecule per one mole of the component (a) having two SiH groups in one molecule (b An excess of more than 1 mol and less than 10 mol, preferably more than 1 mol and 5 mol or less) of the component can be obtained by the addition reaction in the presence of a hydrosilylation reaction catalyst.

  As the hydrosilylation reaction catalyst, known ones can be used. For example, carbon powder carrying platinum metal, platinum black, second platinum chloride, chloroplatinic acid, reaction product of chloroplatinic acid and monohydric alcohol, complex of chloroplatinic acid and olefins, platinum bisacetoacetate, etc. Platinum-based catalysts; platinum-based catalysts such as palladium-based catalysts and rhodium-based catalysts. The addition reaction conditions, the use of a solvent, and the like are not particularly limited, and may be performed under known conditions.

  As described above, since an excess molar amount of the component (b) is used relative to the component (a) in the preparation of the component (A), the component (A) is an addition reactivity derived from the structure of the component (b) It has two carbon-carbon double bonds in one molecule.

  Moreover, when using what has addition-reactive carbon-carbon double bond as (B) component etc. which are mentioned later, (A) component origin which occupies in the whole addition-reactive carbon-carbon double bond in the composition of this invention The proportion of the addition-reactive carbon-carbon double bond is preferably 20 to 100 mol%, more preferably 40 to 100 mol%.

  The component (A) of the present invention can be used singly or in combination of two or more.

[(B) component]
The component (B) of the present invention has a hydrogen atom bonded to at least two silicon atoms in one molecule, and is a group selected from a (meth) acrylic group, a carbonyl group, an epoxy group, an alkoxysilyl group and an amide group Organosilicon compounds that do not have The SiH group in the component (B) is added by hydrosilylation reaction with the addition-reactive carbon-carbon double bond in the component (A) to give a cured product of a three-dimensional network structure. The component (B) does not have a group selected from (meth) acrylic group, carbonyl group, epoxy group, alkoxysilyl group and amido group, and in this respect, at least one of these groups described later (E) component is to be distinguished.
As a component (B), the following (i)-(iii) can be used, for example.

(I) Organohydrogenpolysiloxane represented by the following average composition formula (10)
R ¹ _a H _b SiO _{[(4-ab) / 2]} (10)
(Wherein, R ¹ is each independently an unsubstituted or substituted C ¹ to C 12, particularly 1 to 6 monovalent hydrocarbon group other than an alkenyl group, and a and b each satisfy 0.7 ≦ a ≦ 2) .1, 0.01 b b b 1 and 0.8 a a + b 2.7 2.7)

Specific examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than the alkenyl group in R ¹ in the average composition formula (10) include, for example, methyl, ethyl, propyl, isopropyl and butyl Alkyl groups such as tert-butyl, pentyl, isopentyl, hexyl and sec-hexyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl and o-, m- and p-tolyl; benzyl and 2-phenylethyl And one or more hydrogen atoms bonded to carbon atoms in these groups are substituted with a halogen atom, cyano, an epoxy ring-containing group, etc., for example, chloromethyl, 3-chloropropyl, 3 Halogenated alkyl groups such as 3,3,3-trifluoropropyl; 2-cyanoethyl group; 3-glycidic acid Pill group, and the like.
Among these, in particular, a methyl group or a phenyl group is preferable because it is easy to industrially produce and easily available.

(I) The viscosity of component is not particularly limited, is preferably from 0.1~100,000mm ² / s, more preferably 0.5~500mm ² / s.

(Ii) Addition reaction product of vinyl norbornene and / or diallyl bisphenol A and cyclic organohydrogenpolysiloxane Further, as the component (B), for example, it is represented by the following structural formula (11) or the following structural formula (12) An addition reaction product obtained by hydrosilylation reaction between the component (b) and / or diallyl bisphenol A and the cyclic organohydrogenpolysiloxane can be used.

［式中、Ｚは前記Ｙで表される基または下記構造式（１３）で表される基であり、Ｚ’は前記Ｙ’で表される基または下記構造式（１４）で表される基であり、Ｍｅはメチル基を示す。ｓは０〜１００、好ましくは１〜１０の整数であり、ｔは１〜１００、好ましくは１〜２０の整数であり、ｑおよびｒはそれぞれ独立に０〜３の整数であり、それぞれの環状シロキサン部位におけるｑとｒの合計は独立に２または３である。

（式中、アスタリスク（＊）はケイ素原子との結合部位を示す。）

（式中、アスタリスク（＊）はケイ素原子との結合部位を示す。）］

[Wherein, Z is a group represented by the above Y or a group represented by the following structural formula (13), and Z ′ is a group represented by the above Y ′ or represented by the following structural formula (14) And Me represents a methyl group. s is an integer of 0 to 100, preferably 1 to 10, t is an integer of 1 to 100, preferably 1 to 20, q and r are each independently an integer of 0 to 3, and each cyclic The sum of q and r at the siloxane site is independently 2 or 3.

(In the formula, the asterisk (*) indicates a bonding site to a silicon atom.)

(In the formula, the asterisk (*) represents a bonding site to a silicon atom.)]

(Ii) The viscosity of the component is not particularly limited, is preferably from 0.1~100,000mm ² / s, more preferably 0.1~3,000mm ² / s, more preferably 0. It is 5-500 mm < ² > / s.

（式中、ｑ、ｒは上記と同様である。Ｍｅはメチル基を示す。）
で表される環状シロキサンとをヒドロシリル化反応触媒の存在下で付加反応させて得ることができる。 The compound represented by the formula (11) or (12) is a compound of the above-mentioned (b) component and / or diallyl bisphenol A, and the following formula (15)

(In the formula, q and r are as defined above. Me represents a methyl group.)
Can be obtained by addition reaction with the cyclic siloxane represented by formula (II) in the presence of a hydrosilylation reaction catalyst.

  As the hydrosilylation reaction catalyst, those described above can be used, and the addition reaction conditions, the use of a solvent, and the like are not particularly limited, and may be performed under known conditions.

  In the above reaction, the amounts used of the component (b), diallyl bisphenol A and the cyclic siloxane represented by the above formula (15) are relative to the number of moles of olefin contained in the component (b) and / or diallyl bisphenol A Preferably, the molar ratio of the cyclic siloxane represented by the above formula (15) is 0.9 to 1.1 times.

（上記式中、Ｍｅはメチル基、Ｐｈはフェニル基を示す。） (Iii) SiH Group-Containing Silane Compound As the component (B), the following silane compounds can be used in addition to the components (i) and (ii).

(In the above formula, Me represents a methyl group and Ph represents a phenyl group.)

(Iii) the viscosity of the components is not particularly limited, is preferably from 0.1~100,000mm ² / s, more preferably 0.5~500mm ² / s.

  The component (B) of the present invention can be used singly or in combination of two or more.

  The compounding amount of the component (B) is such that the amount of hydrogen atoms bonded to silicon atoms is 0.5 to 2.0 per mole of the addition-reactive carbon-carbon double bond of the component (A) in the composition of the present invention The amount which becomes a mole is preferable, More preferably, it is an amount which will be 0.8-1.5 mol.

  The proportion of hydrogen atoms bonded to silicon atoms derived from the component (B) in the total hydrogen atoms bonded to silicon atoms in the composition of the present invention is preferably 20 to 100 mol%, more preferably 40 to 100 mol%. It is mol%. When the compounding amount of the component (B) is in such a range, a cured product having sufficient hardness can be obtained.

[(C) ingredient]
The platinum group metal catalyst for hydrosilylation reaction of the component (C) is inactive under light shielding and is irradiated with light having a wavelength of 200 to 500 nm to be converted into an active platinum catalyst to be contained in the component (A). It is a catalyst for promoting the hydrosilylation reaction of the addition-reactive carbon-carbon double bond and the silicon-bonded hydrogen atom in the component (B).

As a specific example of such (C) component, ((eta) ⁵ -cyclopentadienyl) trialiphatic platinum compound, its derivative (s), etc. are mentioned. Particularly preferred among these are cyclopentadienyltrimethylplatinum complexes, methylcyclopentadienyltrimethylplatinum complexes and their cyclopentadienyl-modified derivatives. Further, bis (β-diketonato) platinum compounds are also mentioned as examples of suitable (C) component, and among them, particularly preferable ones are bis (acetylacetonato) platinum compounds and derivatives thereof in which the acetylacetonato group is modified. It is.

  The compounding amount of the component (C) is not limited as long as it accelerates the curing (hydrosilylation reaction) of the composition, relative to the total mass of the components (A) and (B) of the composition. The amount of platinum group metal atoms in this component is preferably 0.01 to 500 ppm by mass, more preferably 0.05 to 100 ppm, and particularly preferably 0.01 to 50 ppm. .

[(D) component]
The component (D) is a reaction control agent, and when the resin composition is prepared or applied to a substrate, it is optionally added as necessary to prevent thickening and gelation before heat curing. You may
Specific examples thereof include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclohexanol, ethynyl Methyl decyl carbinol, 3-methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl- 1-trimethylsiloxycyclohexane, bis (2,2-dimethyl-3-butynoxy) dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,1,1,5 Examples thereof include 3,3-tetramethyl-1,3-divinyldisiloxane, preferably 1-ethynylcyclohexanol and ethynyl. Methyl decyl carbinol is 3-methyl-1-butyn-3-ol.

  The compounding amount of the component (D) is preferably 0.01 to 2.0 parts by mass, particularly preferably 0.01 to 0.1 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B). It is a mass part. Within such a range, the effect of reaction control is sufficiently exhibited.

[(E) ingredient]
The component (E) is an adhesion promoter for providing the composition of the present invention with adhesion to a substrate, and can be used as needed. This component is an organic compound containing at least one or a plurality of functional groups consisting of one or more (meth) acrylic groups, carbonyl groups, epoxy groups, alkoxysilyl groups and amide groups in one molecule, Specific examples are as follows.
Component (E) is distinguished from component (B) (component (iii)) in that it has the above-mentioned functional group.

  Vinyl trimethoxysilane (trade name: KBM-1003, Shin-Etsu Chemical Co., Ltd. product), γ- (glycidyloxypropyl) trimethoxysilane (trade name: KBM) as a specific example of an adhesion assistant containing an organosiloxane skeleton -403, Shin-Etsu Chemical Co., Ltd. product, gamma- (methacryloxypropyl) trimethoxysilane (brand name: KBM-503, Shin-Etsu Chemical Co., Ltd. product), etc. are mentioned.

  Moreover, the siloxane compound etc. which are shown by following Structural formula are mentioned. In the following formulae, Me represents a methyl group.

  Furthermore, allyl glycidyl ether, vinylcyclohexene monoxide, diethyl 2-allyl malonate, allyl benzoate, diallyl phthalate, tetraallyl pyromellitic acid ester (trade name: TRIAM 805, as an example of an adhesion auxiliary containing no organosiloxane skeleton) Wako Pure Chemical Industries, Ltd., triallyl isocyanurate and the like can be mentioned.

  Only one type of component (E) may be used, or a plurality of types may be used in combination. The compounding amount is preferably 0.05 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B).

[Other ingredients]
The composition of the present invention contains, in addition to the components (A) to (C) and optionally (D) and (E), other components exemplified below as long as the object of the present invention is not impaired. It may be
For example, thixotropy control agents such as fumed silica; reinforcing agents such as crystalline silica; antioxidants; light stabilizers; heat resistance improvers such as metal oxides and metal hydroxides; colorants such as titanium oxide; alumina Thermal conductivity-imparting filler such as crystalline silica; Viscosity modifier such as non-reactive silicone oil having no reactive functional group; Conductivity-imparting agent such as metal powder such as silver and gold; Pigment for coloring And dyes.

The ultraviolet curable resin composition of the present invention can be applied to various substrates and used as a coating material or an adhesive.
As the base material, those used in the fields of composite materials, metal members, plastic members, ceramic members, casings or members for electrical applications, electronic applications, optical applications, etc., those used in the fields of casting, adhesion, and sealing are used It is possible. The composition of the present invention can also be used on a substrate activated by known pretreatment steps such as primer treatment, plasma treatment, excimer light treatment and the like.

In curing the ultraviolet curable resin composition of the present invention, light having a wavelength of 200 to 500 nm, preferably 200 to 370 nm, is used to photoactivate the platinum catalyst to initiate a curing reaction. From the standpoint curing rate and discoloration of the composition, irradiation intensity is preferably 30~2,000mW / cm ^2, the irradiation dose is preferably from 150~10,000mJ / cm ^2. 10-60 degreeC is preferable at the temperature at the time of irradiation, More preferably, it is 20-40 degreeC.

  When the UV curable resin composition of the present invention is heated and cured, the curing temperature is not particularly limited, but after the UV curable resin composition is irradiated with UV light, the temperature is 60 to 150 ° C., particularly 60 to 100 ° C. It is preferable to cure for ~ 120 minutes, in particular for 30 to 60 minutes.

  EXAMPLES The present invention will be specifically described below by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following formulas, Me is methyl and Ph is phenyl.

[Examples 1-1 to 1-3, Comparative Examples 1-1 to 1-3]
The following (A)-(E) component was mixed in the compounding quantity (mass part) shown in Table 1, and the ultraviolet curable resin composition was prepared.

Component (A) (A-1) Mixture of polymers wherein m in the structural formula (1) is 1 to 5 (content ratio of addition reactive carbon-carbon double bond 0.40 mol / 100 g)

（Ｂ−４）下記構造式で表される化合物（２３℃における粘度：０．５ｍｍ²／ｓ、ケイ素原子結合水素原子の含有量：０．０１０モル／ｇ）

(B) Component (B-1) Molecular chain both terminal trimethylsiloxy group blocked diphenyl siloxane / methyl hydrogen siloxane copolymer (viscosity at 23 ° C .: 21 mm ² / s, content of silicon-bonded hydrogen atoms: 0.0063 Mol / g)
(B-2) Z 'in the structural formula (12) is a group represented by Y', t is 1 to 11, q and r are each independently an integer of 0 to 2, and each is A mixture of an addition reaction product of vinyl norbornene and tetramethyl cyclotetrasiloxane (the viscosity at 23 ° C .: 2,500 mm ² / s, a silicon-bonded hydrogen atom) in which the sum of q and r in the cyclic siloxane moiety is independently 2 Content of: 0.63 mol / g)
(B-3) Compound represented by the following structural formula (viscosity at 23 ° C .: 1.8 mm ² / s, content of silicon-bonded hydrogen atom: 0.0092 mol / g)

(B-4) Compound represented by the following structural formula (viscosity at 23 ° C .: 0.5 mm ² / s, content of silicon-bonded hydrogen atoms: 0.010 mol / g)

(C) Component (C-1) A toluene solution of methylcyclopentadienyltrimethylplatinum complex having a content of platinum element of 0.5% by mass

Comparative component (C'-2) A toluene solution of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in which the content of platinum element is 0.5% by mass

(D) component (D-1) ethynyl methyl decyl carbinol

(E) Component (E-1) Compound Represented by the Following Structural Formula

(E-2) a compound represented by the following structural formula

[Gelation time of composition]
With respect to each composition obtained, using a UV-LED lamp with a wavelength of 365 nm, ultraviolet light was irradiated at 23 ° C. so as to have an irradiation intensity of 100 mW / cm ² and a dose of 3,000 mJ / cm ² .
After irradiating each composition with ultraviolet light under the above conditions, the composition was placed in a rheometer set at 80 ° C., and the gelation time of the composition was evaluated from the rise time of the torque. The results are shown in Table 1.

[Examples 2-1 to 2-3, Comparative Examples 2-1 to 2-3]
With respect to each resin composition obtained in Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-3, using a UV-LED lamp with a wavelength of 365 nm, the irradiation intensity is 100 mW / cm at 23 ° C. ^The ultraviolet light was irradiated to ² and a dose of 3,000 mJ / cm ² .
Each composition was irradiated with ultraviolet light under the above conditions, and then the composition was cured under conditions of 80 ° C. for 1 hour.
[Appearance of cured product]
The appearance (the presence or absence of wrinkles) of the cured product when the obtained cured product was cooled to 23 ° C. was visually evaluated. The results are shown in Table 2.

[hardness]
The hardness of the cured product used for the above-mentioned appearance evaluation was measured with a JIS hardness meter durometer type D. The results are shown in Table 2.

[Shear adhesion]
After irradiating each composition with ultraviolet light under the above conditions, the composition is sandwiched between two adherends (aluminum plate or polyphthalamide (Amodel A-4122 manufactured by Solvay)) so that the thickness is 80 μm, 80 ° C., The composition was allowed to cure under the conditions of 1 hour, the resulting cured product was cooled to 23 ° C., and the shear adhesion was measured. The results are shown in Table 2.

  As shown in the results of Examples 1-1 to 2-3, the ultraviolet curable resin composition of the present invention has high hardness and adhesiveness in a short time even under relatively mild curing conditions (80 ° C., 1 hour). The cured product was obtained, and the appearance of the cured product was also good. On the other hand, in Comparative Examples 1-1 to 2-3 using a catalyst that is not a platinum catalyst activated by light, it takes longer to cure and hardness compared to the corresponding Examples 1-1 to 2-3. And the adhesion was also inferior.

[Example 3-1, Comparative Example 3-2]
The compositions of Example 1-1 and Comparative Example 1-1 were respectively filled in the following LED packages, and were irradiated with ultraviolet light at 23 ° C. so that the irradiation intensity was 100 mW / cm ² and the dose was 3,000 mJ / cm ^2. The composition was cured at 100 ° C. for 30 minutes.

LED package 1: SMD 5050 (manufactured by I-CHIUN PRECISION INDUSTRY)
LED package 2: SMD3020 (I-CHIUN PRECISION INDUSTRY)
LED package 3: BXCD2630 (made by Bridgelux)

Thermal shock resistance
The obtained test piece is subjected to a reflow test condition of 260 ° C. for 3 minutes, and then subjected to a thermal shock test in which one cycle of temperature conditions of −40 ° C. for 30 minutes and 150 ° C. for 30 minutes is performed. It was determined whether or not the sealing material later cracked and peeled off from the LED element. The results are shown in Table 3.

  As shown in the results of Example 3-1, the LED package sealed with the composition obtained in Example 1-1 was subjected to the reflow test and the thermal shock test for all three test pieces. Peeling of the cured product and occurrence of cracks were not observed, and had excellent mechanical properties and adhesiveness even when exposed to high temperature conditions. On the other hand, peeling of the cured product (Comparative Example 3-1) using the composition obtained in Comparative Example 1-1 with the LED package occurred in a reflow test at 260 ° C. for 3 minutes.

Claims (9)

(A) Polymer Represented by the Following Structural Formula (1):

[Wherein, X is each independently a divalent group represented by the following structural formula (2), and Y is each independently a monovalent represented by any of the following structural formulas (3) to (5) And Y ′ each independently represents a divalent group represented by the following structural formula (6) or (7), and Me represents a methyl group. m is an integer of 0-12.

(In the formula, the asterisk (*) indicates a bonding site to a silicon atom.)

(In the formulas (3) to (7), the asterisk (*) represents a bonding site to a silicon atom, and the configuration at each asymmetric carbon may be either cis (exo) or trans (endo). )]
(B) Organosilicon compounds having hydrogen atoms bonded to at least two silicon atoms in one molecule and having no group selected from (meth) acrylic group, carbonyl group, epoxy group, alkoxysilyl group and amide group ,
(C) A UV curable resin composition containing a platinum group metal catalyst activated by light having a wavelength of 200 to 500 nm. The ultraviolet curable resin composition according to claim 1, wherein the component (C) is a (η ⁵ -cyclopentadienyl) trialiphatic platinum compound or a bis (β-diketonato) platinum compound. The ultraviolet curable resin composition according to claim 1 or 2, wherein the component (B) is at least one selected from the following (i) to (iii).
(I) Organohydrogenpolysiloxane represented by the following average composition formula (10):
R ¹ _a H _b SiO _{[(4-ab) / 2]} (10)
(Wherein, R ¹ is each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than an alkenyl group, and a and b each satisfy 0.7 ≦ a ≦ 2.1, 0. 01 ≦ b ≦ 1, and 0.8 ≦ a + b ≦ 2.7.
(Ii) SiH group-containing addition reaction product obtained from vinyl norbornene and / or diallyl bisphenol A and cyclic organohydrogenpolysiloxane (iii) SiH group-containing silane compound The ultraviolet curable resin composition according to claim 3, wherein the component (ii) is represented by the following formula (11) or (12).

[Wherein, Z is a group represented by the above Y or a group represented by the following structural formula (13), and Z ′ is a group represented by the above Y ′ or represented by the following structural formula (14) And Me represents a methyl group. s is an integer of 0 to 100, preferably 1 to 10, t is an integer of 1 to 100, preferably 1 to 20, q and r are each independently an integer of 0 to 3, and each cyclic The sum of q and r at the siloxane site is independently 2 or 3.

(In the formula, the asterisk (*) indicates a bonding site to a silicon atom.)

(In the formula, the asterisk (*) represents a bonding site to a silicon atom.)] The ultraviolet curable resin composition according to claim 3 or 4, wherein the component (iii) is selected from compounds represented by the following formula.

(Wherein, Me represents a methyl group and Ph represents a phenyl group)   Furthermore, the adhesive agent contains at least one group selected from one or more of (meth) acrylic group, carbonyl group, epoxy group, alkoxysilyl group and amide group in one molecule (E). The ultraviolet curable resin composition of any one of -5.   The adhesive agent which consists of an ultraviolet curable resin composition of any one of Claims 1-6.   The hardened | cured material of the ultraviolet curable resin composition of any one of Claims 1-6.   The manufacturing method of the hardened | cured material made to heat and harden | cure at 60-150 degreeC, after irradiating an ultraviolet-ray to the ultraviolet curable resin composition of any one of Claims 1-6.