JP5203592B2 - Transparent resin composition - Google Patents

Description

  The present invention relates to a transparent resin composition, and more particularly, to a moisture curable modified silicone resin-based resin composition (modified silicone resin-based moisture curable transparent resin composition) having a transparent film after curing.

The modified silicone resin-based moisture curable resin composition is mainly used for adhesives and sealants. In general, polyoxyalkylene polymer having hydrolyzable silyl group, which is a modified silicone resin, calcium carbonate for the purpose of reinforcement, hydrolyzable silane having amino group as an organic group for the purpose of adhesion, dehydration A composition in which an agent and a curing catalyst are added is known. However, this resin composition becomes opaque due to calcium carbonate. When this is opaque, when this is used for an adhesive or a sealing material, for example, an adhesive portion or a sealing portion of a transparent adherend such as polyvinyl chloride, an acrylic resin, a polycarbonate resin, or glass, or an adhesive body This is not preferable because the protruding portion of the film becomes opaque and the appearance is impaired.
In order to solve the opacity caused by calcium carbonate, the resin composition using fine silica powder instead of calcium carbonate is transparent in the liquid state (before curing), but the cured product becomes cloudy because of the amino group-containing silane. Again, transparency is significantly impaired.

  There is a method in which an amino group-containing silane that is an adhesion-imparting agent is not added in order to make a cured modified silicone resin-based resin composition a cured product. However, this resin composition has a drawback of poor adhesion. For this reason, it is necessary to treat the surface of the adherend with a primer or the like in advance, and there is a disadvantage that the work process becomes complicated.

As a resin composition that solves each of the above-mentioned drawbacks, for example, a modified silicone resin-based resin composition that has good adhesiveness and is transparent as in Patent Document 1 below has been proposed.
That is, the resin composition disclosed in Patent Document 1 is a mixture of a polyoxyalkylene polymer having a hydrolyzable silyl group and an acrylic ester and / or methacrylic ester copolymer having a hydrolyzable silyl group. , Hydrophobic fine powder silica and a silane coupling agent having an amino group (synonymous with hydrolyzable silane having an amino group as an organic).
Japanese Patent No. 3435351

  However, acrylic esters and / or methacrylic ester copolymers having hydrolyzable silyl groups are expensive, and there is a problem that adhesives and sealing materials using these are also expensive.

  As a result of diligent research to solve the above-mentioned problems, the present inventor did not use the acrylic ester and / or methacrylic ester copolymer as a moisture-curable resin component, but was available at a lower cost. An object of the present invention is to provide a transparent resin composition that has excellent transparency, good adhesion, and is inexpensive when only a polyoxyalkylene polymer having a silyl group is used.

In order to solve the above problems, the transparent resin composition of the present invention is a hydrolyzable silane having an amino group as an organic group with respect to 100 parts by weight of a polyoxyalkylene polymer having a crosslinkable hydrolyzable silyl group. 3 to 50 parts by weight , a total of 1 to 500 parts by weight of at least one of a styrene resin and a xylene resin, and 0.1 to 100 parts by weight of silica fine powder.

  In addition, by adding silica fine powder to the resin composition, a reinforcing effect is given to the cured product, and the cohesive strength of the cured product can be increased.

  Furthermore, since the silica fine powder is surface-treated with a hydrophobic group, an increase in viscosity can be suppressed.

  The resin composition obtained by the present invention has excellent transparency and good adhesiveness. And, when only the polyoxyalkylene polymer having a hydrolyzable silyl group is used as the moisture curable resin component, the acrylic ester and / or the methacrylate ester copolymer having a hydrolyzable silyl group is used. It can be manufactured at a lower cost.

Embodiments according to the present invention will be described below.
First, the polyoxyalkylene polymer portion which is the molecular skeleton of the polyoxyalkylene polymer (A) having a crosslinkable hydrolyzable silyl group used in the present invention basically has the chemical formula 1, that is, “Chemical Formula 1”. Is shown.

In the above-mentioned “Chemical Formula 1”, R ¹ is a divalent organic group. Particularly preferred is a hydrocarbon group having 3 to 4 carbon atoms. For example, a methyl ethenyl group, an ethyl ethenyl group, an isobutylenyl group, a butenyl group, etc. are mentioned. This molecular skeleton may be one type of repeating unit or two or more types of repeating units. In particular, a polyoxypropylene skeleton in which R ¹ is a methylethenyl group is preferable.

  The hydrolyzable silyl group in the polymer A is represented by the chemical formula 2, that is, “Chemical Formula 2”.

In the above “Chemical Formula 2”, R ² represents a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms or a triorganosiloxy group. For example, an alkyl group such as a methyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, a triorganosiloxy group such as trimethylsiloxy, and the like. Of these, a methyl group is particularly preferred.
X represents a hydrolyzable group such as a hydroxyl group or an alkoxy group. Specific examples include substituents such as hydroxyl groups, halogens such as chlorine, alkoxy groups such as methoxy groups, acyloxy groups, amino groups, amide groups, mercapto groups, and alkenyloxy groups. In particular, a methoxy group or an ethoxy group is preferable from the viewpoint of handling. a is 0, 1, or 2, b is 0, 1, 2, or 3, and each represents an integer that does not take a = b = 0. n represents an integer of 0 to 18. In particular, an integer of n = 0, b = 1, 2, or 3 is preferable from the viewpoint of economy.

From the viewpoint of curability, the number of hydrolyzable silyl groups in the polymer A is preferably 1 or more, more preferably 1.1 or more, and particularly preferably 1.5 or more on the molecular terminal. Further, the number average molecular weight of the polymer A is preferably 500 to 30,000.
The polymer A can be produced by a known method as disclosed in, for example, JP-A No. 63-112642. The polymer A specifically includes, for example, products manufactured by Kaneka Corporation, MS Polymer (registered trademark), Silyl (registered trademark), products manufactured by Asahi Glass Co., Ltd., Exester (registered trademark), and the like. These are commercially available and can be used.

  On the other hand, the hydrolyzable silane (B) having an amino group as an organic group used in the present invention is represented by Chemical Formula 3, that is, “Chemical Formula 3”.

In the above “Chemical Formula 3”, R ³ and R ⁴ represent hydrogen or an organic group. Examples of the organic group include an alkyl group such as a methyl group, an aryl group such as a phenyl group, and an alkyl group having a substituent such as an aminoethyl group. R ³ and R ⁴ may be the same or different. R ⁵ is a divalent organic group. R ² and X are the same as R ² and X in Chemical Formula ² . n represents 1, 2, or 3. As the hydrolyzable silane, 3-aminopropyltrimethoxysilane _{^{(R 3 = R 4 = H}} , R 5 = CH 2 CH 2 CH 2, X = OCH 3, n = 3) and N-(2-aminoethyl ) = 3-aminopropyltrimethoxysilane _{^{(R 3 H, R 4 =}} H 2 NCH 2 CH 2, R 5 = CH 2 CH 2 CH 2, X = OCH 3, n = 3) , and the like.
The amount of the silane B, compared Polymer A100 parts, 3-50 parts by weight good preferable.

  Furthermore, the styrene resin (C) used in the present invention is a styrene analog such as styrene, styrene substituted at the α-position such as α-methylstyrene, styrene substituted with a benzene ring such as vinyltoluene, and the like. And those obtained by polymerizing single or plural homologues, and those obtained by copolymerizing styrene, styrene analogues and homologues with aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, etc. I can give you. The styrenic resin can be appropriately selected from commercially available ones.

Examples of the xylene resin (D) used in the present invention include a reaction product of xylene and formaldehyde, a reaction product of mesitylene and formaldehyde, a reaction product of xylene, phenol and formaldehyde. The xylene resin can be appropriately selected from commercially available ones.
The styrene resin C and the xylene resin D may be used alone or in combination, or the styrene resin C and the xylene resin D may be used in combination.
The total amount of styrene resin C and xylene resin D is preferably 1 to 500 parts by weight, and more preferably 5 to 100 parts by weight, based on 100 parts by weight of polymer A.

Examples of the silica fine powder (E) used in the present invention include fumed silica and silica airgel. The silica fine powder E may be all or partly surface-treated with a hydrophobic group. When the surface of the silica fine powder is treated with a hydrophobic group, the increase in viscosity can be suppressed.
Examples of the silica fine powder surface-treated with a hydrophobic group include those obtained by treating an untreated silica fine powder with an organosilicon compound. Examples of the organosilicon compound include dimethyldichlorosilane, hexamethyldisilazane, dimethylsiloxane, and trimethoxyoctylsilane. An untreated silica fine powder and a surface-treated silica fine powder can be used in combination.
The addition amount of the silica fine powder E is preferably 0.1 to 100 parts by weight, and more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the polymer A.

  In addition, the transparent resin composition of the present invention includes, for example, a curing catalyst, a diluent, a dehydrating agent, an anti-aging agent, an ultraviolet absorber, a light stabilizer, and a silane coupling agent other than having an amino group as an organic group. A known additive such as can be added.

Examples of the curing catalyst include known modified silicone resins such as organic tin, inorganic tin, organic titanate, amine, phosphate ester, reaction product of phosphate ester and amine, polyvalent carboxylic acid, and polyvalent carboxylic acid anhydride. A curing catalyst can be used. As the diluent, known diluents such as phthalate esters and polyoxyalkylenes can be used.
Furthermore, as the dehydrating agent, known dehydrating agents such as vinyl alkoxysilane, alkyl alkoxysilane, orthosilicate ester, anhydrous sodium sulfate, and zeolite can be used. Furthermore, as the silane coupling agent, a silane coupling agent having an organic group having a glycidyl group other than an amino group, a methacryloxy group, a mercapto group or the like can be used.
Although the Example of this invention is described below, this invention is not limited to this Example.

  Exester S3430 (modified silicone resin having a hydrolyzable silyl group-only modified silicone resin: manufactured by Asahi Glass Co., Ltd.) 100 g, FTR (registered trademark) 8080 (styrene resin: manufactured by Mitsui Chemicals, Inc.) 50 g, While kneading with a self-revolving stirrer, dehydration was performed under reduced pressure at 120 ° C.

  After cooling, 2 g of ethyl silicate 28 (tetraethoxysilane: Colcoat Co., Ltd.), 3 g of KBM603 (N- (2-aminoethyl) 3-aminopropyltrimethoxysilane: Shin-Etsu Chemical Co., Ltd.), No. 3 g of 918 (reaction product of dibutyltin oxide and 2-ethylhexyl phthalate: manufactured by Sankyo Gosei Co., Ltd.) was added and stirred until uniform to obtain a resin composition.

  Excerster S3430 100g, Aerosil (registered trademark) 300 (silica fine powder: Nippon Aerosil Kogyo Co., Ltd.) 5g, FTR8080 10g, kneaded with a self-revolving stirrer, reduced pressure at 120 ° C And dehydrated. After cooling, 2 g of ethyl silicate 28, 3 g of KBM603, 3g of 918 was added. After stirring until uniform, it was taken out to obtain a resin composition.

  Exster S3430 100g, Aerosil R972 (silica fine powder surface-treated with hydrophobic group: Nippon Aerosil Kogyo Co., Ltd.) 10g, FTR8080 10g, 120 ° C while kneading with a revolving stirrer Under reduced pressure, dehydration was performed. After cooling, 2 g of ethyl silicate 28, 3 g of KBM603, 3g of 918 was added. After stirring until uniform, it was taken out to obtain a resin composition.

  Exoster S3430 100g, Aerosil R972 10g, Nicanol (registered trademark) Y1000 (xylene resin: Mitsubishi Gas Chemical Co., Ltd.) 10g, kneaded with a self-revolving stirrer, reduced pressure at 120 ° C And dehydrated. After cooling, 2 g of ethyl silicate 28, 3 g of KBM603, 3g of 918 was added. After stirring until uniform, it was taken out to obtain a resin composition.

  Excerster S3430 (100 g), Aerosil R972 (10 g), FTR8080 (5 g), Nikanol Y1000 (5 g) were kneaded with a revolving stirrer and dehydrated under reduced pressure at 120 ° C. After cooling, 2 g of ethyl silicate 28, 3 g of KBM603, 3g of 918 was added. After stirring until uniform, it was taken out to obtain a resin composition.

  Dehydration was performed by reducing the pressure at 120 ° C. while kneading 100 g of Exester S3430 and 10 g of Aerosil R972 with a self-revolving stirrer. After cooling, 2 g of ethyl silicate 28, 3 g of KBM603, 3g of 918 was added. After stirring until uniform, it was taken out to obtain a resin composition (shown in “Comparative Example 1” in Table 2).

  Dehydration was performed by reducing the pressure at 120 ° C. while kneading 100 g of Exester S3430 and 10 g of Aerosil R972 with a self-revolving stirrer. After cooling, 2 g of ethyl silicate 28, no. 3g of 918 was added. After stirring until uniform, it was taken out to obtain a resin composition (shown in “Comparative Example 2” in Table 2).

  Dehydration was performed under reduced pressure at 120 ° C. while kneading with 100 g of Exester S3430, 10 g of Aerosil R972, 10 g of FTR8080, and a revolving stirrer. After cooling, 2 g of ethyl silicate 28, no. 3g of 918 was added. After stirring until uniform, it was taken out to obtain a resin composition (shown in “Comparative Example 3” in Table 2).

About each resin composition obtained above, confirmation of transparency and confirmation of adhesiveness were performed in the following procedures.
That is, the transparency was confirmed visually by bonding the glass plates with the resin composition obtained above and curing. Moreover, the confirmation of adhesiveness was performed as follows. Rigid polyvinyl chloride plates having a width of 25 mm and a length of 50 mm were bonded to each other so as to have an adhesive area of a width of 25 mm and a length of 12.5 mm. After curing at room temperature for 7 days, the tensile shear strength was measured at a tensile rate of 50 mm / min to confirm the adhesion.

  The results of the above confirmations are shown in “Table 1” and “Table 2”. In addition, in transparency, (circle) represents transparency and x represents opaqueness.

  The resin compositions obtained from “Examples 1 to 5” all had excellent transparency and exhibited good adhesiveness. In “Comparative Example 1” to which styrene resin and xylene resin were not added, the adhesiveness was good, but it was opaque. “Comparative Examples 2 to 3” to which no amino group-containing silane was added had good transparency but poor adhesion.

Claims (2)

3-100 parts by weight of hydrolyzable silane having an amino group as an organic group with respect to 100 parts by weight of a polyoxyalkylene polymer having a crosslinkable hydrolyzable silyl group, at least of styrene resin and xylene resin and 1 to 500 parts by weight of one in total, silica fine powder transparent resin composition characterized by containing 0.1 to 100 parts by weight.   The transparent resin composition according to claim 1, wherein at least a part of the silica fine powder is surface-treated with a hydrophobic group.