JP2012052025A - Thermosetting resin composition and cured product of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which has a resin raw material having sufficient compatibility and from which a cured product, which has excellent transparency and resistance to thermal coloration, high hardness, and little surface tackiness and to which neither dust nor fingerprints can attach easily, is obtained; and to provide the cured product of the same.SOLUTION: The thermosetting resin composition contains (A) an organic compound including at least two carbon-carbon double bonds having reactivity with an SiH group, in one molecule, (B) a chain polyorganosiloxane with a weight-average molecular weight of 500-10,000 including at least two SiH groups in one molecule, (C) a compatibilizer, and (D) a hydrosilylation catalyst.

Description

  The present invention relates to a thermosetting resin composition and a cured product thereof.

  Conventionally, acrylic resins that are excellent in transparency and light resistance have been widely used as optical member resins. However, a cured product using an acrylic resin is excellent in transparency and light-coloring resistance, but has a problem in heat-resistant coloration, and further improvement in characteristics has been demanded. On the other hand, the resin for optical members used in the field of optical and electronic equipment is required to have a mounting process on an electronic substrate or the like, heat resistance under high temperature operation and mechanical characteristics, and epoxy resin has been widely used.

  Incidentally, in recent years, the use of high-intensity laser light, blue light, and near-ultraviolet light is spreading in the field of optical and electronic equipment, and a resin that is more excellent in transparency, heat resistance, and light resistance than ever is required. In general, epoxy resins have high transparency in the visible range, but sufficient transparency is not obtained in the ultraviolet to near ultraviolet range. On the other hand, the epoxy resin using alicyclic bisphenol A diglycidyl ether has a problem that it is easily colored by heat or light although it has a relatively high transparency in the ultraviolet to near ultraviolet region. . Therefore, for example, Patent Document 1 and Patent Document 2 disclose methods for reducing impurities that are one of the causes of coloring contained in alicyclic bisphenol A diglycidyl ether.

  In recent years, a cured product using a silicone resin has high transparency from the ultraviolet to the visible region, and is excellent in light coloring resistance and heat coloring resistance. However, silicone resin has high moisture permeability, low adhesion, high coefficient of linear expansion, and is soft, so it cannot produce molded products with complicated shapes, and it is prone to dust and fingerprints. there were.

  In order to improve these problems, for example, Patent Document 3 discloses a method of substituting a part of the methyl group of the dimethylsiloxane skeleton of the silicone resin, which causes softness, with a phenyl group.

  In addition, silicone resins are generally poorly compatible with organic compounds, and even when polyorganohydrogensiloxane and an organic compound having a carbon-carbon double bond are cured, a transparent and uniform cured product can be obtained by phase separation. There was no problem. For example, as a method of combining an organic resin and an inorganic substance containing silicon, there are a sol-gel method in the resin, a method of peeling a clay layer in the resin, and the like. However, these methods have significant problems in terms of water precipitation and transparency as the reaction proceeds.

  In order to solve the above problem, for example, Patent Document 4 proposes an organic modified siloxane as an organic curing agent having a hydrosilyl group in the molecule. The curing agent generally has good compatibility with an organic compound having a carbon-carbon double bond.

JP 2003-171439 A JP 2004-75894 A JP 2004-292807 A JP-A-3-95266

  However, there is room for improvement in the hue of the resin whose coloring is reduced by the methods of Patent Documents 1 and 2 and the like. Moreover, the silicone resin obtained by patent document 3 etc. does not necessarily have long-term reliability, and there exists a subject in heat-resistant coloring especially. Furthermore, the organically modified siloxane obtained in Patent Document 4 and the like has sufficient compatibility particularly when a highly polar organic compound is used as a component having a carbon-carbon double bond reactive with a hydrosilyl group. There is a problem that there is no problem, and it is necessary to design and select a compatible material in accordance with the structure of the component having the carbon-carbon double bond. Moreover, since organic modified siloxane is a special compound and it cannot be said that various things are easily available, it has the problem that industrial practicality is low.

  The present invention has been made in view of the above circumstances, and the resin raw material has sufficient compatibility, is excellent in transparency and heat-resistant colorability, has high hardness and little surface tack, and is hard to adhere to dust and fingerprints. It aims at providing the thermosetting resin composition which can obtain a thing, and its hardened | cured material.

  The present invention includes (A) an organic compound having at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and (B) a weight average molecular weight of 500 to 10,000. Provided is a thermosetting resin composition containing a chain polyorganosiloxane having at least two SiH groups therein, (C) a compatibilizing agent, and (D) a hydrosilylation catalyst.

  In such a thermosetting resin composition, the resin raw material has sufficient compatibility, and the obtained cured product is excellent in transparency and heat-resistant coloration, has high hardness, has little surface tack, and is free from dust and fingerprints. Hard to stick.

The component (A) and the component (B) are preferably incompatible with each other and become uniform when the component (C) is added.
In this specification, the term “compatible” is used to describe a mixture of two or more components that remain clear after separation for about 24 hours at about 25 ° C. without separation of the layers. Used for. The term “incompatible” is also used to describe a mixture of two or more components that mix thoroughly and leave turbid or separate layers after standing at about 25 ° C. for about 24 hours.

  The component (A) is preferably an organic compound having at least one group selected from the group consisting of an alicyclic aliphatic hydrocarbon group, a chain aliphatic hydrocarbon group, and a heterocyclic group.

  It is preferable that at least two of the carbon-carbon double bonds in the component (A) are carbon-carbon double bonds derived from an allyl group.

  The component (A) preferably has an isocyanurate skeleton.

  The component (C) has a molecular weight of less than 500, preferably a compound having a siloxane bond, more preferably an organosiloxane compound, and an organosiloxane compound having at least two SiH groups in one molecule. It is particularly preferred.

  When (C) component is the said compound, compatibility with (A) component and (B) component, reactivity, transparency of cured | curing material, heat resistance, and light resistance can be improved more.

  The equivalent ratio (carbon-carbon double bond / SiH group) of the carbon-carbon double bond in component (A) and the sum of the SiH groups in components (B) and (C) is 0. It is preferable that the ratio is 1 / 1.0 to 0.5 / 1.0.

  The present invention heats the thermosetting resin composition, the carbon-carbon double bond having reactivity with SiH groups in the thermosetting resin composition, a part or all of the SiH groups, A cured product obtained by reacting is provided.

  In the thermosetting resin composition of the present invention, the resin raw material has sufficient compatibility, there is no precipitate accompanying the reaction, and the cured product obtained by reacting the thermosetting resin composition is transparent. Excellent in heat resistance and heat-resistant coloring, high hardness, low surface tack, and difficult to get dust and fingerprints. Therefore, the cured product can be suitably used for applications such as protection, sealing or adhesion of light emitting diode elements, wavelength change or adjustment, or lenses. It can also be used as various optical materials such as lens materials, optical device or optical component sealing materials, display materials, electronic devices or insulating materials for electronic components, and coating materials.

  Hereinafter, the present invention will be described in more detail. The thermosetting resin composition of the present invention comprises (A) an organic compound having at least two carbon-carbon double bonds reactive with SiH groups in one molecule (hereinafter referred to as “component (A)” in some cases). And (B) a chain polyorganosiloxane having a weight average molecular weight of 500 or more and 10,000 or less and having at least two SiH groups in one molecule (hereinafter sometimes referred to as “component (B)”), (C) a compatibilizing agent (hereinafter sometimes referred to as “component (C)”) and (D) a hydrosilylation catalyst (hereinafter sometimes referred to as “component (D)”).

((A) component)
The component (A) is not particularly limited as long as it is an organic compound having at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule. However, the organic compound does not include a siloxane unit (Si—O—Si) such as a polysiloxane-organic block copolymer or a polysiloxane-organic graft copolymer, and C, H, N, O, It is preferable that it contains only S and halogen.

  Examples of the carbon-carbon double bond having reactivity with the SiH group include a carbon-carbon double bond derived from a (meth) acryl group, an allyl group, a vinyl ether group, a vinyl group and the like. Furthermore, it is preferable that at least two of the carbon-carbon double bonds in the component (A) are allyl group-derived carbon-carbon double bonds. The component (A) preferably has an isocyanurate skeleton. The bonding position of the carbon-carbon double bond having reactivity with the SiH group of the component (A) is not particularly limited, and may be present anywhere in the molecule.

  The number of carbon-carbon double bonds having reactivity with the SiH group of the component (A) may be two or more per molecule. When the number of carbon-carbon double bonds reactive with the SiH group of the component (A) is 1 or less per molecule, even if it reacts with the component (B), it will only become a graft structure but not a crosslinked structure. . The component (A) is preferably an organic compound having at least one group selected from the group consisting of an alicyclic aliphatic hydrocarbon group, a chain aliphatic hydrocarbon group, and a heterocyclic group. Moreover, it is preferable that the molecular weight of (A) component is 80-5000.

  Examples of such component (A) include dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, vinyl (meth) acrylate, dicyclopentadiene dimethanol di (meth). Acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (Meth) acrylate, 1,10-decanediol di (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, bisphenol A ethylene oxide (EO) adduct di (Meth) acrylate, (Meth) acrylic compounds such as limethylolpropane tri (meth) acrylate, allyl compounds such as triallyl isocyanurate, cyclohexanedimethanol divinyl ether, dicyclopentenyl vinyl ether, dicyclopentadiene dimethanol divinyl ether, dicyclopentadienediol divinyl ether , Vinyl ether compounds such as tricyclodecane dimethanol divinyl ether, tricyclodecanediol divinyl ether, hydrogenated bisphenol A divinyl ether, vinyl compounds such as vinyl crotonate, divinyl adipate, dimethylsiloxane divinyl, trivinylcyclohexane, limonene, 1 , 5-hexadiene, 1,8-nonadiene, butadiene, polybutadiene and other compounds containing double bonds other than those mentioned above. It is. Among these, triallyl isocyanurate and its derivatives are more preferable from the viewpoint that the obtained cured product is less colored and has high light resistance. These can be used alone or in combination of two or more.

（式中、ｍは４≦ｍ≦１４０を満たす整数を示す。）

（式中、ｐ、ｑは４≦ｐ＋ｑ≦１４０、０≦ｐ、４≦ｑ≦１４０を満たす整数を示す。） ((B) component)
Component (B) is a chain polyorganosiloxane having a weight average molecular weight of 500 or more and 10,000 or less and having at least two SiH groups in one molecule. Examples of the component (B) include organohydrogensiloxanes represented by the following general formula (1) or (2). These can be used alone or in combination of two or more.

(In the formula, m represents an integer satisfying 4 ≦ m ≦ 140.)

(In the formula, p and q are integers satisfying 4 ≦ p + q ≦ 140, 0 ≦ p, 4 ≦ q ≦ 140.)

In this specification, the weight average molecular weight is measured by gel permeation chromatography (GPC) using a calibration curve with standard polystyrene, and the measurement conditions are as follows.
<GPC conditions>
Equipment used: Hitachi L-6000 (Hitachi, Ltd.)
Column: Gel pack GL-R420 + Gel pack GL-R430 + Gel pack GL-R440 (3 in total) [All are trade names manufactured by Hitachi Chemical Co., Ltd.]
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 1.75 ml / min Detector: L-3300RI [Hitachi, Ltd.]

((C) component)
The component (C) is a compatibilizing agent that can improve the compatibility between the component (A) and the component (B). The component (C) has a molecular weight of less than 500, preferably a compound having a siloxane bond, more preferably an organosiloxane compound, and an organosiloxane compound having at least two SiH groups in one molecule. More preferably. The organosiloxane compound refers to an organic compound having at least one siloxane bond. Examples of the component (C) include 1,1,3,3-tetramethyldisiloxane, 1,3-bis (dichloromethyl) -1,1,3,3-tetramethyldisiloxane, 1,1,3. , 3,5,5-hexamethyltrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, cyclotrisiloxane, methylhydrosiloxane oligomer , And organosiloxane compounds such as hydrosiloxane oligomers, from the viewpoints of compatibility and reactivity of the component (A) and the component (B), and transparency, heat resistance, and light resistance of the cured product, 1,3,5,7-tetramethylcyclotetrasiloxane and 1,3,5,7,9-pentamethylcyclopentasiloxane are preferred.

((D) component)
The hydrosilylation catalyst as the component (D) of the present invention is a complex having a central metal and is not particularly limited as long as it has a catalytic activity for the hydrosilylation reaction. Examples of the central metal include platinum, iron, aluminum, palladium, ruthenium, and rhodium. Among these, a hydrosilylation catalyst whose central metal is platinum is preferable. Examples of the hydrosilylation catalyst whose central metal is platinum include, for example, platinum (0) -2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane complex, platinum carbonylcyclovinylmethyl. Examples thereof include a siloxane complex (OSSKO catalyst), a platinum N divinyltetramethyldisiloxane complex (KARSTEDT catalyst), a platinum cyclovinylmethylsiloxane complex (ASHBY-KARSTEDT catalyst), and a platinum octanal / octanol complex (LAMOREAUX catalyst).

  In addition to the above essential components, the thermosetting resin composition includes a curing retarder, a hindered amine light stabilizer, a phenolic or phosphorus antioxidant, an ultraviolet absorber, an inorganic filler, an organic filler, and a coupling. Agents, adhesion promoters, polymerization inhibitors, plasticizers, mold release agents, antistatic agents, flame retardants, and the like may be added.

  The component (A) and the component (B) are preferably incompatible with each other and become uniform when the component (C) is added. The equivalent ratio (carbon-carbon double bond / SiH group) of the carbon-carbon double bond in component (A) and the sum of the SiH groups in components (B) and (C) is 0.1. /1.0 to 0.5 / 1.0 is preferable. It is preferable that the compounding quantity of (C) component in a thermosetting resin composition is 1-200 mass parts with respect to a total of 100 mass parts of (A) component and (B) component. The compounding amount of the component (D) in the thermosetting resin composition is not particularly limited as long as it is an effective amount as a catalyst, but as a metal atom with respect to the total mass of the components (A) to (C). 1 to 500 ppm is preferable.

  In the thermosetting resin composition, the above components (A), (B) and (C) are heated in the presence of the component (D), and a carbon-carbon double bond having reactivity with the SiH group, A cured product can be obtained by reacting a part or all of the SiH groups, that is, by performing a hydrosilylation reaction. The components (A) to (D) are preferably mixed in advance before heating. The reaction temperature of the curing reaction by hydrosilylation is preferably 50 ° C to 150 ° C. When the reaction temperature is less than 50 ° C., curing is insufficient, and when it exceeds 150 ° C., the cured product tends to be colored.

  As described above, the cured product obtained from the thermosetting resin composition of the present invention described above is excellent in transparency and heat-resistant colorability, has high hardness and little surface tack, and is less susceptible to dust and fingerprints. Therefore, the cured product can be suitably used for applications such as protection, sealing or adhesion of light emitting diode elements, wavelength change or adjustment, or lenses. It can also be used as various optical materials such as lens materials, optical device or optical component sealing materials, display materials, electronic devices or insulating materials for electronic components, and coating materials.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples of the present invention. However, the present invention is not limited to these examples, and various modifications can be made without departing from the technical idea of the present invention. Can be changed.

（ｎは平均値で２５である。）の化学式で表されるハイドロジェンポリジメチルシロキサン６０質量部、（Ｃ）成分として１，３，５，７−テトラメチルシクロテトラシロキサン（和光純薬株式会社製、以下、「ＴＭＣＴＳ」という）１５０質量部、（Ｄ）成分として白金（０）−２，４，６，８−テトラメチル−２，４，６，８−テトラビニルシクロテトラシロキサン錯体０．７質量部を加えて、これらを均一になるまで混合した。次いで、厚さ１ｍｍ及び３ｍｍとなるように底が平らなガラス容器に混合液を入れ、オーブンで１００℃１時間、１２０℃２時間、１５０℃１時間加熱し、厚さ１ｍｍ及び３ｍｍの硬化物を得た。 Example 1
In a 50 mL screw tube, 100 parts by mass of triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd., hereinafter referred to as “TAIC”) as component (A),

(N is an average value of 25) 60 parts by mass of hydrogen polydimethylsiloxane represented by the chemical formula, 1,3,5,7-tetramethylcyclotetrasiloxane (Wako Pure Chemical Industries, Ltd.) as component (C) 150 parts by mass (hereinafter referred to as “TMCTS”), platinum (0) -2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane complex as component (D) 7 parts by weight were added and mixed until uniform. Next, the mixed solution is put into a glass container having a flat bottom so as to have a thickness of 1 mm and 3 mm, and heated in an oven at 100 ° C. for 1 hour, 120 ° C. for 2 hours, and 150 ° C. for 1 hour to obtain a cured product having a thickness of 1 mm and 3 mm. Got.

(Example 2)
In a 50 mL screw tube, 100 parts by mass of TAIC as component (A), 60 parts by mass of hydrogen polydimethylsiloxane as in Example 1 as component (B), 1,1,3,3-tetramethyl as component (C) 150 parts by mass of disiloxane (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as “TMDS”), platinum (0) -2,4,6,8-tetramethyl-2,4,6,8- as component (D) Tetravinylcyclotetrasiloxane complex 0.7 parts by mass was added and mixed until uniform. Next, the mixed solution is put into a glass container having a flat bottom so as to have a thickness of 1 mm and 3 mm, and heated in an oven at 100 ° C. for 1 hour, 120 ° C. for 2 hours, and 150 ° C. for 1 hour to obtain a cured product having a thickness of 1 mm and 3 mm. Got.

(Comparative Example 1)
In Comparative Example 1, a compound was blended and a curing reaction was performed under the same conditions as in Example 1 except that the component (C), which is a compatibilizing agent, was not added. However, a uniform and transparent cured product was not obtained.

[Evaluation of cured product]
About the hardened | cured material obtained in the said Examples 1-2, the heat-resistant coloring property, hardness, and fingerprint adhesiveness (tack of hardened | cured material surface) were measured by the method shown below.

(Heat resistant colorability)
The cured product (1 mm thickness) was placed in an oven at 150 ° C. and allowed to stand for 72 hours. The light transmittance at 460 nm before and after heating and the yellowness (YI) were measured with V-570 manufactured by JASCO Corporation. The colorability was evaluated. The results are shown in Table 1.

(hardness)
For the cured product (3 mm thick), Shore hardness A using a hardness meter (dual meter, type A) and Shore hardness D using a hardness meter (dual meter, type D) were measured. The results are shown in Table 1.

(tack)
After pressing the surface of the cured product with a finger, the tack was evaluated based on the presence or absence of fingerprints. The results are shown in Table 1.

Claims (10)

(A) an organic compound having at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule;
(B) a chain polyorganosiloxane having a weight average molecular weight of 500 or more and 10,000 or less and having at least two SiH groups in one molecule;
(C) a compatibilizer;
(D) a hydrosilylation catalyst;
Containing thermosetting resin composition.   The thermosetting resin composition according to claim 1, wherein the component (A) and the component (B) are incompatible with each other and become uniform when the component (C) is added.   The component (A) is an organic compound having at least one group selected from the group consisting of an alicyclic aliphatic hydrocarbon group, a chain aliphatic hydrocarbon group, and a heterocyclic group. Thermosetting resin composition.   The thermosetting resin composition according to claim 1, wherein at least two of the carbon-carbon double bonds in the component (A) are allyl group-derived carbon-carbon double bonds.   The thermosetting resin composition according to claim 1, wherein the component (A) has an isocyanurate skeleton.   The thermosetting resin composition according to claim 1, wherein the component (C) is a compound having a molecular weight of less than 500 and having a siloxane bond.   The thermosetting resin composition according to claim 1, wherein the component (C) is an organosiloxane compound having a molecular weight of less than 500.   The thermosetting resin composition according to claim 1, wherein the component (C) is an organosiloxane compound having a molecular weight of less than 500 and having at least two SiH groups in one molecule.   The equivalent ratio (carbon-carbon double bond / SiH group) of the carbon-carbon double bond in the component (A) and the sum of the SiH groups in the components (B) and (C) is 0. The thermosetting resin composition according to any one of claims 1 to 8, which is 1 / 1.0 to 0.5 / 1.0.   The thermosetting resin composition according to any one of claims 1 to 8 is heated, and in the thermosetting resin composition, a carbon-carbon double bond having reactivity with a SiH group, and a SiH group. Hardened | cured material obtained by making one part or all part react.