JPS62174247A - Vinylidene fluoride resin composition - Google Patents

Abstract

PURPOSE:To improve solvent resistance, adhesion, chemical resistance (particularly acid resistance), etc., by mixing a vinylidene fluoride polymer with an acrylic polymer having hydrolyzable silyl groups. CONSTITUTION:This vinylidene fluoride resin compsn. contains a vinylidene fluoride polymer (A), an acrylic polymer (B) having hydrolyzable silyl groups and an org. solvent (C) capable of dissolving the vinylidene fluoride polymer (A) at a temp. of not higher than the b.p. of the solvent. Examples of the component B are homopolymers of a 1-4C alkyl (meth)acrylate or copolymers thereof with a minor quantity of other copolymerizable ethylenically unsaturated monomer, said homopolymers and said copolymers having hydrolyzable silyl groups. As the component A, vinylidene fluoride homolpolymer is particularly preferred.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a resin composition containing a vinylidene fluoride polymer and a hydrolyzable silyl group-containing acrylic resin composition. Polymer and vinyl fluoride 1
7-Den polymer! The present invention relates to a vinylidene fluoride resin composition composed of a resistant organic solvent.

(Prior art) Vinyl fluoride IJ-dene polymers have excellent weather resistance, ultraviolet resistance,
It is used for molding and paint because it has good corrosion resistance and stain resistance.

(Problems to be Solved by the Invention) However, fluorinated pyridine-based polymers do not inherently require adhesion, and in order to improve this, a special method of mixing thermoplastic acrylic polymers has been proposed. Kosho 45-1036
It is disclosed in Publication No. 3. The resin composition obtained by this method has improved adhesion, but since the acrylic polymer is thermoplastic, it has the disadvantage of poor solvent resistance, and is particularly difficult to use when heated. It was noticeable when

Furthermore, there are methods to improve this drawback, such as mixing thermosetting acrylic resin, but there are drawbacks such as insufficient compatibility, and even if compatibility is good, chemical resistance is significantly reduced. Yes, it was not practical.

(Means for Solving the Problems) As a result of intensive research in order to obtain a vinylidene fluoride resin composition free from the above-mentioned drawbacks, the present inventors have developed an acrylic polymer containing a hydrolyzable silyl group. It was discovered that when mixed, a vinylidene fluoride resin composition having excellent solvent resistance, adhesion, and chemical resistance (especially acid resistance) can be obtained, and the present invention has been completed.

That is, the present invention comprises a vinylidene fluoride polymer (A), a hydrolyzable silyl group-containing acrylic polymer (B),
The present invention provides a vinylidene fluoride resin composition characterized by containing a vinylidene fluoride polymer (A) and an organic solvent (C) that can dissolve the vinylidene fluoride polymer (A) at a temperature below its boiling point. Examples of the vinylidene fluoride polymer (A) used in the above include homopolymers of vinylidene fluoride and copolymers containing vinylidene fluoride as a main component,
Among these, those with a vinylidene fluoride content of 31% or more and comonomers containing fluoroolefin units such as tetrafluoroethylene, hexafluoropropylene, vinyl sulfide, etc. are preferable. Combination is preferred.

The hydrolyzable silyl group-containing acrylic polymer (B) used in the present invention includes homopolymers and copolymers of alkyl (meth)acrylates in which the alkyl group has 1 to 4 carbon atoms; ) Using acrylate as the main component, copolymerizable with other ethylenically unsaturated substances, such as monoolefinic and diolefinic hydrocarbons, halogenated monoolefinic hydrocarbons, and halogenated monoolefinic hydrocarbons. Acrylic polymers such as copolymers consisting of monoolefinic and diolefinic hydrocarbons, unsaturated esters of organic and inorganic acids, unsaturated acid esters, unsaturated nitriles, unsaturated acids, etc. Examples include those having a hydrolyzable silyl group within. Among them, formula (X), -a(R+) aSt (
In the formula, R1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, and X is a halogen atom, an alkoxy group, an acyloxy group, an iminoxy group, a phenoxy group, a thioalkoxy group, an amino group, an alkenyloxy group. , an alkoxyalcokyne group, and a represents an integer of 0 or 1 to 2. Preferably.

The method for producing this acrylic polymer (B) is not particularly limited, but it is usually produced by known methods broadly classified into the following two methods. One of them is hydrosilane (X) 3-a
(Rt) a SiH (in the formula, R1, Another method is to carry out a hydrosilylation reaction using the formula (X) s'-a (R+) a 5iR2 (wherein R1, This is a method of copolymerizing a silane compound represented by (representing an organic group having the following) and an acrylic monomer. Among these, the latter method is preferred, and particularly preferred polymers obtained by this method include those obtained by radical polymerization of 6-methacryloxypropyltrimethoxysilane and an acrylic monomer.

The usage ratio (A)/(B) of vinylidene fluoride polymer (A) and acrylic polymer (B) used in the present invention is usually 2 o/s O to 9.0/10. range,
Among these, the range of 40,760 to 70,150 is preferable because it can improve adhesion, solvent resistance, and chemical resistance without deteriorating the inherent properties of the hepta-vinyliso/based polymer, such as weather resistance.

In addition, in the present invention, the weather resistance, ultraviolet resistance, corrosion resistance, stain resistance, solvent resistance, adhesion, and chemical resistance of the coating film obtained from the resin composition of the present invention are not significantly reduced. As far as possible, a resin such as an alkyl (meth)acrylate copolymer having an alkyl group having 1 to 4 carbon atoms can be contained in the acrylic polymer (B) in an amount of 60% by weight or less and 11t% or less.

Examples of the organic solvent (C) used in the present invention include those that can dissolve the vinyl fluoride IJ-dene polymer (A) at a temperature below the boiling point, especially those with a boiling point of 280°C or below, especially 18
Preferably, the temperature is 0°C or lower. For example, cyclohexanone, inophorone, mesityl oxide, diacet/alcohol, methyl ethyl ketone, etc. Kettle a: alkyl and aliphatic and aromatic carboxylic acids such as dimethyl adipate, diethyl succinate, dimethyl phthalate, 2-methquine ethyl acetate, etc. Alcoquine alkyl esters;
Glycol ethers and esters such as diethylene glycol and monoethyl ether acetate; dioxane, 2
These include cyclic ethers such as tetrahydrofuran; carbonate esters such as ethylene carbonate and propylene carbonate; lactones such as butyrolactone; and amides such as dimethylacetamide and dimethylformamide. Mix and use. Incidentally, if necessary, other organic solvents such as xylene and toluene may be contained in an amount up to 50i1tm% of the total solvent.

The resin composition of the present invention may contain a stabilizer against trace moisture of the hydrolyzable silyl group-containing acrylic polymer (B) and a catalyst for hydrolysis and condensation. As an agent, (X)4-1)
(Rs)bsi (wherein, X is the same as above, R3 is a monovalent organic group having 1 to 12 carbon atoms which may have a functional group,
b represents 0 or an integer from 1 to 6); HC(OR4) s (wherein R4
each independently represents an alkyl group having 1 to 5 carbon atoms), trialkyl orthoformate, R,OH (in the formula, R8
represents an alkyl group having carbons a1 to a4), and these alcohols can be used individually or in combination. Specific examples include tetraethoxysilane, tetramethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, methyltriacetoxysilane, vinyl-
Tris(2-methoxyethoxy)silane, methyl orthoformate, ortho-modified ethyl, methanol, ethanol, 1
-butanol and the like. The amount of this stabilizer used is 10% of the hydrolyzable silyl group-containing acrylic polymer (B)
The amount is usually 0.5 to 75% by weight, preferably 2 to 60% by weight, based on 0 parts by weight.

In addition, a hydrolyzable silyl group-containing acrylic polymer (B)
Any known and commonly used catalyst can be used as the catalyst for the hydrolysis and combination of
- Basic compounds such as butylamine, ethylenediamine, triethylamine, isophoronediamine, imidazole, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate; tetra-1-propyl titanate, tetrabutyl titanate, tin octylate, octylic acid Lead, cobalt octylate, zinc octylate, calcium octylate, lead naphthenate, cobalt naphthenate, dibutyltin diacetate, diptyltin dioctate,
Metal-containing compounds such as dibutyltin dilaurate and dibutyltin maleate: p-)luenesulfonic acid, trichloracetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, phosphate ester of β-hydroxyethyl (meth)acrylate, monoalkyl phosphite, dialkyl Examples include acidic compounds such as phosphorous acid, and particularly preferred are tinned compounds such as dibutyltin diacetate, diptyltin dioctate, dibutyltin dilaurate, and dibutyltin maleate. The amount of this catalyst used is based on the hydrolyzable silyl group-containing acrylic polymer (
B) It is usually in the range of 1 to 10 parts by weight, preferably 0.01 to 5 parts by weight, per 100 parts by weight.

Furthermore, the resin composition of the present invention may contain known organic or inorganic pigments, aluminum, copper, brass, gold,
Various additives such as metal powders such as nickel, ultraviolet absorbers, and antioxidants can be added.

In order to obtain the resin composition of the present invention, the above-mentioned components and additives are mixed and dispersed or dissolved in an organic solvent using a known method such as a dispersion mixer such as a glass bead mill or a homodisper. The non-volatile content concentration is usually in the range of 20 to 80% by weight, preferably 30 to 60% by weight.

1 when using the resin composition of the present invention as a coating composition
! 2! The film curing temperature is suitably in the range of 170 to 250°C; the lower the temperature, the longer the curing time, while the higher the temperature, the shorter the curing time. Especially 18
A range of 0 to 220°C is preferred.

(Effects of the Invention) The vinylidene fluoride resin composition of the present invention thus obtained has excellent solvent resistance, adhesion, and chemical resistance, and also has excellent weather resistance, etc., which vinylidene fluoride polymers inherently have. Since it has the advantage of being retained, it is ideal for coating tiles, exterior steel plates, flues, stoves, tanks, chemical plant equipment, pipes, etc. (Example) Next, the present invention will be described in Examples and This will be explained in more detail with reference to comparative examples. In the following, unless otherwise specified, all parts and parts are based on weight (with the exception of the adhesion rate in the substrate test).

Example 1 50 parts of Kynar-500 (polyvinylidene fluoride manufactured by Pennwalt), methyl methacrylate and T-methacryloxypropyltrimethoxy/silane
t ratio of 80:20) copolymer of quinolene/n-butanol (weight ratio of 70:30) #liquid (non-volatile content: 50%,
Average molecular weight: 110,000, hereinafter referred to as acrylic polymer solution C
B-1]), 100 parts of cyclohexanone, and 12.5 parts of trimethyl orthoformate were dispersed in a glass bead mill for 1 hour. 5 parts of dibutyltin dioctate α was added to the obtained dispersion and mixed to obtain the vinylidene fluoride resin composition of the present invention.

Next, this resin composition was applied to a steel plate by a dipping method, and
Heat curing was performed at ℃ for 50 minutes. The resulting coating film remained unchanged for 4,000 hours using a Tenshine weather meter.
In addition, the adhesion was determined by the substrate test and 100 pieces adhered (100/1).
00) was shown. Further, when the surface condition of the coating film was observed after being immersed in acetone or ethyl acetate heated to 50° C., there was no change, and the solvent resistance was good. Furthermore, after placing concentrated sulfuric acid on the coating film and leaving it for 5 hours, the concentrated sulfuric acid was wiped off and the coating film was inspected. There was no change, and the chemical resistance was also good.

The results are shown in Table-1.

Examples 2 to 5 Vinylidene fluoride resin compositions of the present invention were obtained in the same manner as in Example 1, except that each component was blended as shown in Table 1, and then a coating test was conducted in the same manner. , Example 2
The curing conditions for ~5 are 200°C x 30 minutes) The results are shown in Table 1. The acrylic polymer solution CB-2) used in Example 2 was composed of methyl methacrylate, ethyl acrylate, and T-methacryloxypropyltrimethoxysilane (
xylene/n- copolymer with a weight ratio of 75:10:15)
Butanol (Ii ratio 70:30) solution (non-volatile content 50
%, average molecular weight 15,000).

Comparative Example 1 Kynar soo so part, xylene solution of polymethyl methacrylate (non-volatile content 50, average molecular weight 10.00
0, hereinafter referred to as acrylic polymer solution CB'-1)) 1
00 parts, 80 parts of cyclohegisanone, and 20 parts of dimethyl phthalate were dispersed in a glass beads mill for 1 hour to obtain a vinylidene fluoride resin composition for comparison. This resin composition was applied to a steel plate by a dipping method, and heat-cured at 180° C. for 30 minutes. When the eyelid properties of the obtained coating film were measured in the same manner as in Example 1, the weather resistance and adhesion were good, but the coating film swelled when immersed in warm acetone and ethyl acetate. It occurred and was defective. In addition, the chemical resistance was poor as the coating film swelled when exposed to concentrated sulfuric acid. The results are shown in Table-1.

Comparative Example 2 Kynar 500 50 parts, a xylene/methanol (weight ratio 70:30) solution of a copolymer of methyl methacrylate and N-methylolated acrylamide (weight ratio 80:20) (non-volatile content 50%, average molecular weight 10, 000 (hereinafter referred to as acrylic polymer solution CB'-2)) and 100 parts of cyclohexane 2 were dispersed in a glass beads mill for 1 hour. Paratoluene sulfo/acid 1 is added to the resulting dispersion.
5 parts were added and mixed to obtain a vinylidene phthalide-based m-fat composition for comparison. This resin composition was applied to a steel plate by a dipping method, and heat-cured at 180° C. for 50 minutes. The physical properties of the obtained 6114 were measured in the same manner as in Example 1, and the weather resistance, adhesion, and solvent resistance were good, but the chemical resistance was poor as the coating film swelled when exposed to concentrated sulfuric acid. . The binding is shown in Table-1.

Procedural amendment May 2, 1988 Michibe Uga, Commissioner of the Patent Office1, Indication of the case, Patent Application No. 16429 of 19882, Name of the invention Vinylidene fluoride resin composition 3, Person making the amendment Case Relationship with Patent originator: 3-35-58 Sakashita, Iibashi-ku, Tokyo (288) Representative of Dainippon Ink Chemical Industries, Ltd.
Address: Shigeru Kuni Mura 4, Representative Address: Dainippon Ink Chemical Industry Co., Ltd., 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 Tokyo (03) 272-4511 (Main representative)
12, (8876) Patent Attorney Masaru Takahashi 11, -5-/6, "Detailed Description of the Invention" column 7 of the specification to be amended, Contents of the amendment (1) Line 15 of page 1 of the specification The description is corrected as follows.

"Constructed from a vinyl IJ 7-' polymer and an organic solvent that can dissolve it at a temperature below its boiling point" (2) The statement on page 4, lines 1 and 2 of the specification is corrected as follows.

"and diifine hydrocarbons, organic or non-organic"

Claims (1)

[Claims] An organic solvent that can dissolve the vinylidene fluoride polymer (A), the hydrolyzable silyl group-containing acrylic polymer (B), and the vinylidene fluoride polymer (A) at a temperature below the boiling point (
C) A vinylidene fluoride resin composition comprising: