JP3020600B2 - Copolymer composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a copolymer into which an organosiloxane has been introduced.

[Background of the Invention]

When an organosiloxane is introduced into a copolymer, a film having excellent oxygen permeability, durability and weather resistance can be obtained. Therefore, this type of copolymer has recently been spotlighted in the field of high-performance paints and the like.

[Conventional technology]

Conventionally, for example, the following structural formula A copolymer obtained by copolymerizing an organosiloxane having the above formula with an acrylic ester and / or a methacrylic ester to introduce an organosiloxane has been provided for applications such as paints and adhesives.

[Problems to be solved by the invention]

However, the above-mentioned conventional organosiloxane-introduced copolymer still has sufficient oxygen permeability, durability,
No film having weather resistance has been obtained.

[Means for solving the problem]

The present invention provides the following structural formula as means for solving the above conventional problems. Here, R ₁ , R ₂ , and R ₃ are hydrogen or a methyl group, R ₄ and R ₅ are an alkylene group having 3 or less carbon atoms, R ₆ is a hydrogen or a methyl group or a group having the following structure, Here, R ₇ and R ₈ are an alkylene group having 3 or less carbon atoms, and R ₉ is a hydrogen or methyl group.

 n is an integer of 1 to 200.

It is intended to provide a copolymer composition obtained by copolymerizing an organosiloxane A having the following formula: and another vinyl monomer B copolymerizable with the organosiloxane A.

 Hereinafter, the present invention will be described in more detail.

[Organosiloxane A] The organosiloxane A used in the present invention has the following structural formula.

Specific examples of the organosiloxane A are shown below.

Hereinafter, the organosiloxane is referred to as A-200.

Hereinafter, the above organosiloxane is referred to as A-100.

The above organosiloxanes may be used as a mixture of two or more kinds.

[Vinyl monomer B] Examples of the vinyl monomer B copolymerizable with the organosiloxane include methyl acrylate or methyl methacrylate (hereinafter, referred to as methyl (meth) acrylate, etc.), ethyl (meth) acrylate, and n-propyl. (Meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, 2-ethylhexyl (meth)
Acrylate, cyclohexyl (meth) acrylate,
(Meth) acrylates such as tetrahydrofurfuryl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, fatty acid vinyls such as vinyl acetate and vinyl propionate, aromatic vinyls such as styrene and α-methylstyrene, and acrylonitrile , Nitrile monomers such as methacrylonitrile, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, iso-propyl vinyl ether, n-butyl vinyl ether, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, etc. Halogen-containing monomers, acrylic acid, methacrylic acid, itaconic acid, citraconic acid, atropic acid, β-hydroxyethyl (meth)
Having a functional group such as acrylate, β-hydroxypropyl (meth) acrylate, allyl alcohol, (meth) acrylamide, N-methylol (meth) acrylamide, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyl allyl ether, etc. Vinyl monomer, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane,
Examples thereof include silyl group-containing vinyl monomers such as vinyl tris (β-methoxyethoxy) silane and vinyl trichlorosilane. The above examples do not limit the invention.

Of the above vinyl monomers, particularly desirable for the purposes of the present invention are acrylic esters and / or methacrylic esters.

[Copolymer] The above organosiloxane A and the above vinyl monomer B
Is copolymerized by, for example, solution polymerization, emulsion polymerization or the like, but usually the copolymerization ratio of the organosiloxane A and the vinyl monomer B is 0.5: 99.5 to 30: 7 by weight.
Set to about 0.

(Solution polymerization) Examples of the organic solvent used in the solution polymerization of the present invention include aromatic solvents such as benzene, toluene and xylene, and acetates such as ethyl acetate, n-propyl acetate, iso-butyl acetate and n-butyl acetate. Solvents, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, iso-propanol, n
-Alcohol solvents such as butanol, cellosolve solvents such as ethyl cellosolve and n-butyl cellosolve, chlorinated hydrocarbon solvents such as trichloroethylene and 2.4-dichloroethane, and hydrocarbon solvents such as n-hexane, cyclohexane, gasoline, light oil and kerosene. Solvents and the like are exemplified. Two or more organic solvents may be mixed. The above examples do not limit the invention.

As the polymerization initiator used in the solution polymerization of the present invention,
Organic polymerization initiators such as benzoyl peroxide, lauroyl peroxide, dibutyl hydroperoxide, cumene hydroperoxide, azobisisobutyronitrile, azobisvaleronitrile, or the organic polymerization initiator and ascorbic acid, amine, etc. Redox-based polymerization initiators in combination with the above reducing agents.

The organosiloxane A and the vinyl monomer B
Is mixed in the above-mentioned ratio and solution-polymerized in the above-mentioned organic solvent using the above-mentioned polymerization initiator. The concentration of the monomer mixture in the organic solvent in the solution polymerization is usually about 20 to 70% by weight, and the polymerization initiator is usually about 0.01 to 5% by weight based on the monomer mixture, The polymerization temperature is usually from normal temperature to about 90 ° C. The polymerization is performed in an inert gas atmosphere such as nitrogen gas, if desired.

(Emulsion polymerization) As the surfactant used in the emulsion polymerization of the present invention, for example, any of anionic, nonionic, and cationic surfactants are used. For example, as the anionic surfactant, a higher alcohol sulfate (Na salt or Amine salt), alkyl allyl sulfonate (Na salt), alkyl naphthalene sulfonate, alequif phosphate, dialkyl sulfosuccinate, rosin soap,
Nonionic polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkyl amide, sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester, cationic Examples thereof include trimethylaminoethylalkylamide halides, alkylpyridinium sulfates, alkyltrimethylammonium halides, and the like.For example, compounds having the following general formula Here, R: C ₁₂ , C ₁₈ M: Na, NH ₄ .

Ramo S-120,120A, 180,180A manufactured by Kao Soap Co., Ltd.
Etc. and having the following general formula, Eleminol JS-2 manufactured by Sanyo Chemical Industries, Ltd. Alternatively, Aqualon HS-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. having the following general formula Reactive surfactants having a vinyl group such as are desirable for the present invention. Since the above-mentioned reactive surfactant copolymerizes with the above-mentioned monomer mixture, it hardly affects the water resistance of the obtained copolymer composition. Then, two or more surfactants may be mixed.

Examples of the polymerization initiator used in the emulsion polymerization of the present invention include water-soluble inorganic initiators such as ammonium persulfate, potassium persulfate, sodium persulfate, and sodium perborate;
2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2-methyl-N-
Examples include water-soluble organic initiators such as phenylpropionamidine) dihydrochloride, or redox initiator systems using the above inorganic or organic initiators in combination with reducing agents such as sodium sulfite, sodium bisulfite, sodium hyposulfite, and ascorbic acid. Is done. The above examples do not limit the invention.

The organosiloxane A and the vinyl monomer B
Is mixed with an aqueous solution in which the surfactant is dissolved, and is subjected to emulsion polymerization using the polymerization initiator. The concentration of the monomer mixture in the emulsion polymerization is usually about 20 to 60% by weight, the polymerization initiator is usually about 0.01 to 5% by weight based on the monomer mixture, and the polymerization temperature is usually room temperature. To about 90 ° C. The polymerization is carried out in an inert gas atmosphere such as nitrogen gas if desired.

[Action / Effect]

Organosiloxane A is introduced into the copolymer of the present invention, and exhibits remarkably superior oxygen permeability, durability, weather resistance, and mechanical properties as compared with the copolymer into which other organosiloxane is introduced. The reason is that organosiloxane A
Has --R ₄ --O--R ₅ -or --R ₇ --O--R ₈
This is presumably due to the presence of the ether bond-.

〔Example〕

Example 1 A reactor equipped with a stirrer, a condenser, a thermometer, and a gas inlet tube was charged with 200 parts by weight of water, and 10 parts by weight of a reactive emulsifier JS-2 and 0.8 parts by weight of potassium persulfate were added to the water. Parts by weight and 0.4 parts by weight of sodium bisulfite are dissolved, a monomer mixture having the following composition is dropped over 2 hours while heating and stirring at 70 ° C.

2-ethylhexyl methacrylate 20 parts by weight n-butyl methacrylate 60 メ チ ル methyl methacrylate 15 Ａ A-200 (molecular weight 1350) 5 〃 γ-methacryloxypropyltrimethoxysilane 3 紫外線 ultraviolet absorber 0.5 後 After dropping of the above monomer mixture After further aging at 70 ° C. for 2 hours to complete the reaction, the mixture is cooled to room temperature to obtain an emulsion copolymer No. 1 having a solid content of 33.2% by weight and a viscosity of 50 cps / 25 ° C.

Example 2 Emulsion polymerization is carried out in the same manner as in Example 1 using a monomer mixture having the following composition.

2-ethylhexyl methacrylate 20 parts by weight n-butyl methacrylate 60 メ チ ル methyl methacrylate 10 〃 A-200 (molecular weight 1350) 10 〃 γ-methacryloxypropyl trimethoxysilane 3 紫外線 ultraviolet absorber 0.5 に よ り solid content 33.5 weight by the above emulsion polymerization %, Viscosity 56cps /
An emulsion copolymer No. 2 at 25 ° C. is obtained.

Example 3 In a reactor similar to that of Example 1, 150 parts by weight of xylene and n-
50 parts by weight of butanol are charged and a monomer mixture having the following composition is added dropwise over 2 hours while stirring at 80 ° C. and stirring.

2-ethylhexyl methacrylate 20 parts by weight n-butyl methacrylate 60 メ チ ル methyl methacrylate 15 〃 A-200 5 γ γ-methacryloxypropyltrimethoxysilane 3 紫外線 ultraviolet absorber 0.5 後 After the completion of dropping of the monomer mixture, further 80 ° C. After aging for 3 hours to complete the reaction, the mixture was cooled to room temperature to obtain a solution polymer No. 3 having a solid content of 33.4% by weight and a viscosity of 510 cps / 25 ° C.

Example 4 A solution polymerization was carried out in the same manner as in Example 3 using a monomer mixture having the following composition.

2-ethylhexyl methacrylate 20 parts by weight n-butyl methacrylate 60 メ チ ル methyl methacrylate 10 Ａ A-200 10 γ γ-methacryloxypropyltrimethoxysilane 3 〃 ultraviolet absorber 0.5 に よ り By the above solution polymerization, solid content 33.3% by weight, viscosity 560 cps
A solution polymer No. 4 at / 25 ° C is obtained.

Comparative Example 1 Organosiloxane A-200 used in Example 2
In place of the organosiloxane A 'having the following structural formula
And emulsion polymerization is carried out in the same manner as in Example 2.

The molecular weight of the organosiloxane A 'is 2,000.

By the above emulsion polymerization, solid content 33.2% by weight, viscosity 51 cps /
An emulsion copolymer No. 5 at 25 ° C. is obtained.

Comparative Example 2 Organosiloxane A-200 used in Example 4
The solution polymerization was carried out in the same manner as in Example 4 except that the organosiloxane A 'used in Comparative Example 1 was used instead of
A solution polymer No. 6 having 3.4% by weight and a viscosity of 520 cps / 25 ° C. is obtained.

Comparative Example 3 Emulsion polymerization was carried out in the same manner as in Example 1 using a monomer mixture having the following composition.

2-ethylhexyl methacrylate 20 parts by weight n-butyl methacrylate 60 メ チ ル methyl methacrylate 15 γγ-methacryloxypropyltrimethoxysilane 8 に よ り By the above emulsion polymerization, a solid content of 33.4% by weight and a viscosity of 54 cps /
An emulsion copolymer No. 7 at 25 ° C. is obtained.

Polymer Nos. 1 to 7 obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were applied to a glass plate to a thickness of about 15 μm and dried at room temperature to form a film. Table 1 shows the test results for the above coated plates.

Referring to Table 1, No. 1 to No. 4, which are the copolymers into which the organosiloxane A of the present invention is introduced, are copolymers into which the organosiloxane A 'containing no ether bond is introduced.
No.5 and No.6, superior in oxygen permeability, durability and weather resistance compared to copolymer No.7 which does not introduce organosiloxane,
It can also be seen that a transparent film is provided.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Shoji Oshirodo 687 Arimoto Arimoto, Wakayama-shi, Wakayama Shin Nakamura Chemical Industry Co., Ltd. Development Technology Research Laboratory (56) References JP-A-56-22325 (JP, A) Kaihei 4-190213 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 290/00-290/14 C08L 1/00-101/14 C09D 1/00-201/10 C08F 30/00-30/10 C08F 230/00-230/10 C08G 77/00-77/62

Claims (2)

(57) [Claims] 1. The following structural formula Here, R ₁ , R ₂ , and R ₃ are hydrogen or a methyl group, R ₄ and R ₅ are an alkylene group having 3 or less carbon atoms, R ₆ is a hydrogen or a methyl group or a group having the following structure, Here, R ₇ and R ₈ are an alkylene group having 3 or less carbon atoms, and R ₉ is a hydrogen or methyl group. n is an integer of 1 to 200. A copolymer composition obtained by copolymerizing an organosiloxane A having the formula: and another vinyl monomer B copolymerizable with the organosiloxane A. 2. The copolymer composition according to claim 1, wherein the vinyl monomer copolymerizable with the organosiloxane A is an acrylic ester and / or a methacrylic ester.