KR900005626B1 - Primer composition - Google Patents

Abstract

Primer compsn. comprises (A) 100 pts. wt. of a copolymer obtd. by making (1) acrylic type of formula (I) react with 0.11000 wt.% to (1) of (2) a silane cpd. of formula (II) in presence of a free radical initiator, (B) 0.1-500 pts. wt. of above 1 kind of titanium ester cpd., titanium chelate cpd. and alumininm ester cpd., (C) 0.1-500 pts. wt. of org. silicon cpd. with more than 1 alkyl gp. bonded to the Si atom and (D) 0.1-10000 ppm as the element to component (A) of a platinium, palladium or rhodium cpd. and (E) 250-3500 pts. wt. to total of (A)-(D) of an organic solvent. In formulas, R1 and R2= resp. H or monovalent opt. substd. hydrocarbon gp.; R3= H or monovalent opt. substd. hydrocarbon gp.; R4= opt. substd. hydrocarbon gp.; Q1= C1-6 divalent hydrocarbon gp..

Description

Primer composition

The present invention relates to a primer composition, and more particularly to a primer composition for adhering an addition-reactive liquid silicone rubber cured by room temperature or heating to plastics, glasses and metals.

The liquid silicone rubber cured by the addition reaction includes polyorganosiloxanes having alkenyl groups in the molecule and polyorganosiloxanes having silicon atoms bonded to hydrogen atoms in the molecule from room temperature to 200 ° C in the presence of a platinum-based catalyst. It is cured by heating, and there is no reaction product, and it has excellent properties such as electrical insulation, heat resistance, cold resistance, moisture resistance, and ultraviolet ray resistance, so that electric and electronic materials are used as encap materials and mold materials.

On the other hand, in recent years, as an optical material such as laminated glass and solar cells, acrylic resins and polycarbonate resins have been widely used due to their transparency and other excellent properties.

As a potting material or a cushioning material of such a material, a transparent one of the above-described addition reaction type liquid silicone rubber is used, but in general, the liquid silicone rubber has poor adhesiveness with a plastic material, thus providing a method of providing adhesiveness. It is adopted in various ways.

These methods include adding a silane compound as an additive in a liquid silicone rubber composition and using a primer. As for the former, there is a problem that the type of plastic that can impart adhesiveness in the present state is large.

Moreover, although the various primers are provided as a method by the latter primer, in particular, providing satisfactory adhesiveness with respect to the acrylic resin and polycarbonate resin used for an optical material is not obtained in the present state.

An object of the present invention is to provide a primer capable of imparting good adhesion to addition reaction liquid silicone rubber with respect to plastics, glass, and the like, particularly with respect to acrylic resins and polycarbonate resins.

MEANS TO SOLVE THE PROBLEM The present inventors came to complete this invention, discovering that favorable adhesiveness is provided by the primer of the composition demonstrated below as a result of carrying out research in order to achieve the objective mentioned above.

That is, this invention (A) (1) general formula

An acrylic compound represented by (wherein R ¹ and R ² each represent a group selected from a hydrogen atom and a monovalent substituted or unsubstituted hydrocarbon group),

(2) general formula

Wherein R ³ represents a group selected from a hydrogen atom and a monovalent substituted or unsubstituted hydrocarbon group, R ⁴ represents a monovalent substituted or unsubstituted hydrocarbon group, and Q ¹ represents a divalent hydrocarbon group having ¹ to 6 carbon atoms. Copolymer obtained by reacting a silane compound with 0.1-1,000 weight% of silane compounds of (2) with respect to the acryl-type compound of (1) in presence of a free radical initiator ... 100 weight part

(B) One or two or more kinds of compounds selected from ester compounds of titanium, titanium chelate compounds, aluminum ester compounds, aluminum chelate compounds and iron ester compounds.

(C) A silicon compound having at least one unsaturated bond-containing group in its molecule bonded to a silicon atom ... 0.1-500 parts by weight

(D) Platinum-based, palladium-based or rhodium-based catalyst ... 1 × 10 ^-5 -1.0 parts by weight (amount of 0.1-10,000 ppm in terms of each element of platinum, palladium and rhodium relative to component (A))

(E) Organic solvents ... It is 250-3,500 weight part with respect to 100 weight part of total amounts of (A)-(D) It is related with the primer composition characterized by the above-mentioned.

Component (A) used in the present invention is a copolymer of component (1) and component (2) described below. Acrylic compound of (1) is a general formula

(Where R ¹ and R ² are as described above).

Examples of R ¹ include alkyl groups such as hydrogen atom, methyl group, propyl group, butyl group, amyl group, hexyl group, octyl group, decyl group and dodecyl group; Aryl groups such as phenyl group; Alkyl groups such as β-phenylethyl group and β-phenylpropyl group and substituted hydrocarbon groups such as chloromethyl group, cyanoethyl group and 3,3,3-trifluoropropyl group are exemplified, but are easy to synthesize and easy to handle in an uncured state. It is preferable that it is a hydrogen atom or a methyl group from a point.

In addition, as R <^2> , the same group as R <^1> is used.

As an example of such a (1) component,

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The silane compound of (2) is a general formula

However, R ³ , R ⁴ and Q ¹ are the same as described above. As R ³ , the same group as R ¹ is used, but a hydrogen atom or a methyl group is preferable in view of ease of synthesis.

As R ⁴ , alkyl groups such as methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, octyl group, decyl group and dodecyl group are exemplified, but methyl group, ethyl group and propyl group are preferable in view of ease of synthesis.

Moreover, as Q <^1> , a trimethylene group is the most preferable from the point of the synthesis | combination being easy, and stability.

(2) As an example of a component

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Etc. can be mentioned.

From (1) and (2), when the copolymer is obtained, the compounding ratio of both components is selected in the range of (2) 0.1-1,000% by weight, preferably 10-500% by weight relative to (1). If (2) is less than 0.1% by weight, good adhesion cannot be obtained, and if it exceeds 1,000% by weight, the preservation stability of the composition is deteriorated and the price is disadvantageous. The copolymerization reaction takes place in an organic solvent in the presence of a free group initiator.

Since the reaction temperature is in the range from room temperature to the reflux temperature of the solvent and a suitable reaction time, the temperature at which the half life of the initiator is 1-6 hours, particularly preferably about 4 hours is preferable.

The temperature at which the half-life is about 4 hours depends on the type of initiator, but is 60 for benzoperoxide, 2,4-dichlorobenzoyl peroxide, t-butyl peroxy 2-ethyl hexanoate, azobis isobutyl nitrile, and the like. -90 ° C. As the free group initiator, organic peroxides such as benzoyl peroxide, 2,4-dichloro benzoyl peroxide, di-t-butyl peroxide, t-butyl peroxy 2-ethyl hexanoate, t-butyl perbenzoate and azobis isoiso Azo compounds, such as butyl nitrile, are illustrated.

Although the usage-amount is not specifically limited, About 0.05-1 weight% is preferable with respect to the total amount of (1) and (2).

As an organic solvent used for the reaction mentioned above, Aromatic hydrocarbons, such as benzene, toluene, xylene; Halogenated aromatic hydrocarbons such as chlorobenzene; Alcohols such as methanol, ethanol, propanol and butanol; Esters such as ethyl acetate and propyl acetate; Ketones such as acetone; Ethers such as ethyl ether tetrahydrofuran and the like.

The amount of use is about twice as large as (A) component. Component (B) used in the present invention is one or two or more compounds selected from an ester compound of titanium, a titanium chelate compound, an ester compound of aluminum, an aluminum chelate compound and an ester compound of iron, and the primer composition of the present invention. It is an essential ingredient for the drying, film formation and adhesion function.

As an ester compound of titanium, titanium esters, such as tetra-n-propyl titanate and tetra-n-butyl titanate, and its polymer; As a titanium chelate compound, titanium acetyl acetonate etc. are mentioned; Aluminum isopropylate aluminum-sec-butylate; As an aluminum chelate compound, aluminum tris acetyl acetonate, aluminum tris (ethyl acetate acetate), ethyl acetate acetate aluminum diisopropylate, etc .; Iron naphthenate, iron octenate, etc. are mentioned as an ester compound of iron. The usage-amount of (B) component is 0.1-500 weight part with respect to 100 weight part of (A) component.

If it is less than 0.1 part by weight, the drying property is slow and the adhesiveness is lowered, and if it exceeds 500 parts by weight, the drying property is excessively accelerated and the workability is poor, thereby impairing the safety of the primer composition.

Component (C) used in the present invention is an organosilicon compound having at least one of an unsaturated bond-containing group bonded to a silicon atom, and is roughly classified into an organosilane and an organosiloxane.

Examples of such organic silanes include vinyl triethoxy silane, vinyl tris (2-methoxy ethoxy) silane, vinyl triacetoxy silane, 3-methacryloxy propyl trimethoxy silane and vinyl methyl dimethoxy silane. do.

Examples of the organic siloxane include tetramethyl tetravinyl cyclotetra siloxane, tetramethyl-1,3-divinyl disiloxane, and formulas

And polyorganosiloxanes represented by (wherein R ⁵ and R ⁶ are the same or different aliphatic to aromatic groups, at least one of which is an unsaturated bond-containing group such as vinyl group, methacryloxy group, etc.). .

The component (C) may be used alone or as a mixture of two or more thereof. The usage-amount of (C) component is 0.1-500 weight part with respect to 100 weight part of (A) component.

Outside this range, the adhesion of the primer is poor. Component (D) used in the present invention is a platinum-based, palladium-based or rhodium-based catalyst. Platinum-based catalysts include platinum chloride supported on a carrier such as chloroplatinic acid, a complex salt of platinum and an alcohol, a complex salt of platinum and an olefin, a complex salt of platinum and a ketone, a complex salt of platinum and a vinyl siloxane, and a carrier such as alumina or silica. And platinum hooks and the like are exemplified.

Examples of the palladium-based catalyst include tetrakis (triphenyl phosphine) palladium, a mixture of palladium black and triphenyl phosphine, and the like.

Examples of the rhodium-based catalyst include tetrakis (triphenyl phosphine) rhodium, a mixture of rhodium black and triphenyl phosphine, and the like.

These platinum-based, palladium-based and rhodium-based catalysts may be used alone or in combination.

The usage-amount of (D) component is 0.1-10,000 ppm, Preferably it is 1.0-5,000 ppm in conversion of each element amount of platinum, palladium, and rhodium with respect to (A) component.

If less than 0.1ppm is susceptible to poor curing, special care needs to be taken practically, and if it exceeds 10,000ppm, it is economically disadvantageous.

The organic solvent of component (E) used in the present invention should be volatile and have good wet properties to the adherend, and should dissolve the (A)-(D) components uniformly, dissolve the adherend or damage the adherend. It is necessary to satisfy the conditions such as not giving.

As such an organic solvent, Alcohol, such as methanol, ethanol, isoproline, an alcohol, n-butanol; Aromatic hydrocarbons such as benzene, toluene and xylene; Ketones such as acetone and methyl ethyl ketone; And ester aliphatic hydrocarbons such as ethyl acetate, propyl acetate, and butyl acetate.

These organic solvents may be used alone or as a mixed solvent containing two or more kinds.

The compounding quantity of (E) component is 250-3,500 weight part with respect to 100 weight part of total amounts of (A)-(D). If it exceeds 3,500 parts by weight, the concentration of the components (A)-(D) becomes excessively thin, making it difficult to obtain uniform adhesion. Also, if the content is less than 250 parts by weight, the primer layer on the adhesive surface becomes excessively thick. Falls out.

The primer of this invention is obtained by mixing (A)-(E) component. Furthermore, before use, for example, the two parts may be mixed and divided into two parts consisting of (A) (C) (D) (E) components and (B) (E) components. According to the primer composition of this invention, the favorable adhesiveness which a conventional primer does not have can be obtained at the time of adhesion | attachment of addition reaction type | mold liquid silicone rubber, an acrylic resin, a polycarbonate resin, etc.

For this reason, it is used very widely for a wide use, such as adhering additional silicone rubber to various kinds of plastics.

EXAMPLE

Hereinafter, the present invention will be described according to embodiments. Parts in the examples all indicate parts by weight.

Example 1

50 parts of methyl methacrylate, 10 parts of γ-methyloxypropyl trimethoxy silane, 60 parts of ethyl acetate, and 60 parts of isopropyl alcohol were added thereto, and 0.6 parts of benzoyl peroxide was added thereto, followed by 2 hours at a temperature of 80-85 ° C. The reaction was carried out to obtain a copolymer solution (A ₁ ).

As the compounding ratio shown in the first table in A ₁ , 2-ethyl hexane of chloroplatinic acid containing tetrabutyl titanate, γ-methacryloxypropyl trimethoxysilane, vinyl triethoxy silane, and 2% platinum is used as a solution and solvent. Butyl acetate was added to prepare primer composition X ₁ and comparative primer composition Y ₁ -Y ₄ of the present invention.

These primer compositions X ₁ and Y ₁ -Y ₄ were thinly coated on a methacryl resin plate: acrylic light (trade name: Mitsubishi Rayon Co., Ltd.) with cotton wool, and left to stand at room temperature for 30 minutes. A), (B); Mix the components (A) and (B) for each of TSE 3033 (A), (B) and YE5626 (A), (B) (see "Notes" in Table 1 for details). The degassed thing was inject | poured between two sheets of the above-mentioned primer-treated acrylic plates, and it heated and hardened | cured at 80 degreeC for 2 hours, and obtained the sample for adhesive evaluation. The obtained sample was measured for shear bond strength by a tensile tester with a magnetic recording device. The results are shown in Table 1 together.

TABLE 1

Example 2

Isopropanol solution containing 75% of aluminum-mono-acetylacetonate-bis (ethyl acet acetate) in copolymer solution A ₁ , γ-methacryloxypropyl trimethoxy silane, tetramethyltetravinyl cyclotetra siloxane, 2% Octanol solution of chloroplatinic acid containing platinum, octanol solution of chloroplatinic acid containing 2% rhodium, toluene solution of tetrakis (triphenyl phosphine) rhodium containing 2% rhodium and butyl acetate the primer composition of the present invention were used in amounts shown in Table 2, X _2, X ₃ was prepared.

The primer composition was subjected to the adhesion test in the same manner as in Example 1 except that YE 5626 (A) and (B) were used as the additional liquid silicone rubber and the heat curing conditions of one silicone rubber were set at 80 ° C for 4 hours. .

The results are also shown in Table 2.

TABLE 2

Example 3

Toluene solution of tetrakis (triphenyl phosphine) palladium containing 3 parts of copper catalyst and 2% Pd of 2-ethyl hexane of chloroplatinic acid containing 2% Pt in place of 10 parts of solution in Example 1 A primer composition X ₄ of the present invention was prepared in the same manner as in Example except that parts were used. The primer composition X ₄ was subjected to the adhesion test in the same manner as in Example 1 using YE 5626 (A) and (B) as an additive liquid silicone rubber, and found that the shear bond strength was 13.2 kgf / cm 2 and the cohesive failure rate was 85%. Adhesiveness was shown.

Example 4

45 parts of ethyl methacrylate, 15 parts of γ-methacryloxypropyl trimethoxy silane, 60 parts of butyl acetate, and 60 parts of isopropyl alcohol were added thereto, and 1.0 parts of azobisisobutyl nitrile was added thereto at a temperature of 80-85 ° C. The mixture was reacted for 4 hours to obtain a copolymer solution A ₂ . Tetra in the copolymer solution A ₂ 180 parts (2-ethylhexyl) titanate (with 6% in terms of Fe), 5 parts of octanoic tensan Fe 1 unit, γ- methacryloxypropyl trimethoxysilane 30 parts, vinyl trimethoxysilane A primer was prepared by adding 10 parts of oxysilane, chloroplatinic acid, 10 parts of IPA solution (containing 3% as Pt), 200 parts of ethyl acetate, and 280 parts of butyl acetate.

This was then applied to acrylic resins, nylon resins, epoxy resins and polycarbonate plates and dried in the air at room temperature for 30 minutes.

TSE 3033 (A) and (B) were placed on each of the primer-treated plates as a two-component addition-response silicone rubber, and cured by heating at 70 ° C for 4 hours. Thereafter, these were peeled off by hand and qualitatively examined for adhesion. Both showed cohesive failure in the silicone rubber layer and exhibited good adhesion without peeling off at the interface.

Claims (7)

(A) (1) general formula

(Wherein R ¹ and R ² each represent a group selected from a hydrogen atom and a monovalent substituted or unsubstituted hydrocarbon group), and (2) a general formula

A silane represented by (wherein R ³ represents a hydrogen atom and a monovalent substituted or unsubstituted hydrocarbon group, R ⁴ represents a monovalent substituted or unsubstituted hydrocarbon group Q ¹ represents a divalent hydrocarbon group having ¹ to 6 carbon atoms) Copolymer obtained by reacting the compound with 0.1-1,000 weight% of the silane compound of (2) with respect to the acryl-type compound of (1) in presence of a free radical initiator ... 100 weight part (B) Ester compound of titanium, titanium chelate One or two or more compounds selected from compounds, ester compounds of aluminum, aluminum chelate compounds, and ester compounds of iron. 0.1-500 parts by weight (C) at least one unsaturated bond-containing group in the molecule is bonded to a silicon atom ... 0.1 to 500 parts by weight of an organic silicon compound with (D) a platinum-based, palladium-based or rhodium-based catalyst ... platinum, palladium, about 1.0 × 10 ⁺⁵ -1.0 parts by weight of ((a) component and In terms of each element amount of the rhodium 0.1-10,000ppm) (E) an organic solvent ... (A) - the primer composition, wherein the (D) the total amount relative to 100 parts by weight parts by weight of 250-3500. The primer composition according to claim 1, wherein R ^{1 in} (A) (1) is a hydrogen atom or a methyl group. The primer composition according to claim 1, wherein R ³ in (A) (2) is a hydrogen atom or a methyl group. The primer composition according to claim 1, wherein R ⁴ in (A) (2) is any one of methyl group, ethyl group and propyl. The primer composition according to claim 1, wherein Q ¹ of (A) (2) is a trimethyl group. The primer composition according to claim 1, wherein the compounding amount of (A) (2) is 10-500% by weight based on (A) (1). The primer composition according to claim 1, wherein the compounding amount of (D) is 1.0-5,000 ppm with respect to the component (A).