JPH0629351B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a resin composition having improved stability which is useful as a base resin component for paints, sealing agents, adhesives, films and the like, More specifically, it relates to a resin composition comprising a specific fluoroolefin copolymer and a phosphine compound.

[Problems to be Solved by Prior Art and Present Invention]

In recent years, a fluoroolefin copolymer containing a hydroxyl group has been developed as a solvent-soluble, crosslinkable resin having excellent weather resistance, and has come to be mainly used for paints. However, the fluoroolefin copolymer containing such a hydroxyl group has a drawback that it is inferior in storage stability, thickens with time, and finally gels.

Although a method of adding a specific tertiary amine has been proposed in order to improve such a defect (Japanese Patent Laid-Open No. 28458/1985), it is necessary to add a tertiary amine to obtain sufficient stability by this method. The amount has to be increased, and there is a problem that the resin is markedly colored accordingly.

[Means for solving problems]

Therefore, as a result of intensive studies to solve the above-mentioned problems, the present inventors added a phosphine compound as an additive to significantly improve long-term storage stability without significantly coloring the resin. The present invention has been found and the present invention has been completed.

That is, the present invention provides a resin composition having an improved stability, which comprises (A) a hydroxyl-containing fluoroolefin copolymer and (B) a phosphine compound as essential components.

Here, the fluoroolefin copolymer (A) containing a hydroxyl group described above, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, monofluoroethylene, hexafluoropropylene or perfluoroalkyl trifluoro It refers to a copolymer containing a hydroxyl group bonded to the main chain and / or side chain of a copolymer containing fluoroolefins such as vinyl ether as an essential monomer component. The preferred hydroxyl value of such a copolymer is 5 to 200 mgKOH / g.

Fluoroolefin copolymer containing such a hydroxyl group
(A) is (1) copolymerizing a vinyl monomer having a hydroxyl group with fluoroolefins as described above, or
(2) It is synthesized by a conventionally known method such as saponification of a vinyl ester group-containing polymer obtained by copolymerizing a carboxylic acid vinyl ester with a fluoroolefin, and is particularly synthesized by the method (1). Is convenient.

As the vinyl monomer having a hydroxyl group that can be used when obtaining the copolymer (A) by the method (1), for example, hydroxyalkyl such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether or hydroxyhexyl vinyl ether. Vinyl ethers are particularly preferable, and hydroxyalkyl esters of (meth) acrylic acid such as β-hydroxyethyl (meth) acrylate, β-hydroxypropyl (meth) acrylate and β-hydroxybutyl (meth) alicrete are also copolymerized. It can be used within a range that does not deteriorate the properties. Specific examples of the copolymerizable monomer that can be used for obtaining the copolymer (A) from the above-mentioned fluoroolefins and hydroxyalkyl vinyl ethers include ethyl vinyl ether, n-propyl vinyl ether, iso-propyl vinyl ether, n. -Alkyl vinyl or cycloalkyl vinyl ethers such as -butyl vinyl ether, iso-butyl vinyl ether, t-butyl vinyl ether, lauryl vinyl ether, octadecyl vinyl ether, 2-chloroethyl vinyl ether or cyclohexyl vinyl ether; 2,2,3,3-tetrafluoropropyl vinyl ether, 2,2,3,3,4,4,5,5
-Octafluoropentyl vinyl ether, 2,2,3,3,4,
Fluoroalkyl vinyl ethers such as 4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl vinyl ether, trifluoromethyl vinyl ether, pentafluoroethyl vinyl ether, heptafluoropropyl vinyl ether; acetic acid Vinyl, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl cyclohexanecarboxylate, vinyl benzoate, vinyl β-tert-butylbenzoate, fatty acid carboxylic acid having a branched alkyl group of C _{3 to} C _9. Vinyl esters, vinyl carboxylates such as vinyl laurate or vinyl stearate; olefins or chloroolefins such as ethylene, propylene, vinyl chloride or vinylidene complex; vinyltrimethoxysilane, vinyltris (β-
There are vinylsilanes such as methoxyethoxy) silane.

Cyclohexyl vinyl ether among the above copolymerization components,
It is preferable to use at least one selected from alkyl vinyl ether and vinyl carboxylate as an essential component. For example, copolymers of fluoroolefins, hydroxyalkyl vinyl ethers, and cycloalkyl vinyl ethers and / or alkyl vinyl ethers; copolymers of fluoroolefins, hydroxyalkyl vinyl ethers and vinyl carboxylates; fluoroolefins, Mention may be made of copolymers of hydroxyalkyl vinyl ethers, vinyl carboxylates and cycloalkyl vinyl ethers and / or alkyl vinyl ethers. The quantitative proportions of these copolymerization components are as follows: 10 to 70 mol% of fluoroolefins, 0 to 70 mol% of (cyclo) alkyl vinyl ethers, 0 to 60 mol% of vinyl carboxylates, 1 to 30 mol% of hydroxyalkyl vinyl ethers, and Other copolymerizable monomers are preferably in the proportion of 0 to 30 mol%.

To obtain the copolymer (A) from the fluoroolefin, hydroxyalkyl vinyl ether and a copolymerization component, solution polymerization by a radical polymerization initiator system, emulsion polymerization,
A conventionally known method such as suspension polymerization can be applied.

Next, the phosphine compound (B) which is a stability improver used in the present invention refers to a compound in which two or three organic groups are bonded to one phosphorus atom and has a molecular weight of 62.
~ 1000 compounds. Specific examples of such phosphine compounds include trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, trilaurylphosphine, tristearylphosphine, dimethylphosphine, diethylphosphine, dibutyl. Di- or trialkylphosphines such as phosphine, dioctylphosphine, dilaurylphosphine;
Tris (3-hydroxypropylphosphine, tris (2-cyanoethyl) phosphine, tris (2-methoxyethyl) phosphine, tris (2-chloroethyl) phosphine, tris (2-methoxycarboxyethyl) phosphine, tris [2- (2 -Dimethylaminoethoxy) carbonyl] phosphine, tris (2-
Ethoxycarbonylethyl) phosphine, bis (3-
Di- or tri-substituted alkylphosphines such as hydroxypropyl) phosphine and bis (2-cyanoethyl) phosphine; Alicyclic phosphines such as dicyclopentylphosphine, dicyclohexylphosphine, tricyclopentylphosphine and tricyclohexylphosphine Triphenylphosphine,
Di- or triallyl phosphines such as tris (4-methylphenyl) phosphine, diphenylphosphine, bis (4-methylphenyl) phosphine; tribenzylphosphine, triphenethylphosphine, dibenzylphosphine, diphenethylphosphine Di- or tri-aralkylphosphines such as fins; 1,2-bis (diphenylphosphino) ethane, 1,4
-Bis (diphenylphosphino) butane, 1,6-bis (diphenylphosphino) hexane, 1,2-bis (dimethylphosphino) ethane, 1,4-bis (dimethylphosphino) butane, 1,6-bis (Dimethylphosphino) hexane, 1,2-bis (diethylphosphino) ethane, diphosphines such as 1,4-bis (dibutylphosphino) butane, tetramethylenephosphine, tetramethylene-methylphosphine, the following (I ) Or a phosphine having a phosphorus atom in the ring represented by the formula (II); two or three different phosphorus atoms such as diphenylmethylphosphine, diphenylethylphosphine and phenyldiethylphosphine. There are phosphines with organic groups attached.

The amount of the component (B) used is preferably such that the phosphorus atom is in the range of 0.002 to 1 equivalent per 1000 g of the component (A). If it is less than 0.002 equivalents, the stability is insufficient, and if it exceeds 1 equivalent, coloring of the composition becomes large, and a cured product obtained by adding a curing agent capable of reacting with a hydroxyl group to the composition of the present invention. It is not preferable because the weather resistance of is lowered.

The composition of the present invention comprising the components (A) and (B) may be in the form of a solventless solid type, a solventless liquid or a solution, but it may be used for coating applications. In terms of workability, it is particularly preferable to use a solution. Specific examples of the solvent that can be used when the composition of the present invention is used as a solution include toluene, xylene, and other aromatic hydrocarbons; hexane, octane, cyclohexane, methylcyclohexane, and other aliphatic or finger-ring hydrocarbons; methanol, Alcohols such as ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether; esters such as methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate System; ketone, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Such solvents can be used alone or as a mixture of two or more kinds.

The composition of the present invention may be used as it is or as the case requires, curing agents such as polyisocyanate compounds, amino resins or epoxy resins, other resins such as acrylic resins, polyester resins or alkyd resins, pigments and leveling agents. A coating composition, a sealing agent, an adhesive agent, a composition containing an ultraviolet absorber, an antioxidant, etc.
It can be used for applications such as films.

〔Example〕

Next, the present invention will be described in more detail with reference to Reference Examples, Examples and Comparative Examples. In the following, all parts and% are based on weight unless otherwise specified.

Reference Examples 1 to 5 [Preparation Example of Fluoroolefin Copolymer (A) Containing Hydroxyl Group] In a pressure-resistant stainless steel tube having an inner volume of 1000 m, 330 g of methyl isobutyl ketone and 4.2 g of tert-butyl peroxypivalate were prepared. And a monomer as described in Table 1 were charged, and the mixture was dried at -70 in a dry ice / methanol bath.
After cooling to ℃, nitrogen gas was blown in to replace the air in the pressure resistant tube.

Then, liquefied and collected hexafluoropropylene (HF
Abbreviated as P) or chlorotrifluoroethylene (C
(Abbreviated as TFE) was charged in an amount as described in the same table and sealed. On the other hand, tetrafluoroethylene (T
In the case of using FE) or vinylidene fluoride (abbreviated as VDF), each raw material was charged in the same manner as above, TFE or VDF was press-fitted, hermetically sealed, and then weighed.

After that, each of these pressure-resistant tubes was put in a rotary constant temperature water tank heated to 60 ° C., reacted for 16 hours, then the contents were taken out, and the necessary amount of xylene was added so that the nonvolatile content became 50%. Then, each desired copolymer was obtained. The molecular weights of the obtained copolymers are as shown in Table 1, and the Gardner colors were all 1 or less.

Examples 1 to 5 The ratios shown in Table 2 are fluoroolefin copolymers (A).
And phosphine compound (B) are mixed to obtain 500
Put m in a 1000 m tin can and seal it at 40 ° C.
The Gardner viscosity and Gardner color were measured after storage in a constant temperature bath for 3 months. The storage stability was evaluated by calculating the viscosity ratio after storage for 3 months and the viscosity ratio immediately after mixing. The results are shown in the table.

Comparative Examples 1 to 6 Only the resin solution or the copolymer (A) to which the tertiary amine was added in the ratio shown in Table 2 was stored in the same manner as in the Examples, and the storage stability and the resin color were evaluated.

[Effects of the Invention] As is clear from the above results, the composition of the present invention showed a small increase in viscosity and coloration even after long-term storage, resulting in a significant improvement in storage stability. .

Claims (5)

[Claims] 1. A resin composition comprising a fluoroolefin copolymer (A) having a hydroxyl group and a phosphine compound (B). 2. The copolymer (A) is obtained by copolymerizing fluoroolefin, hydroxyalkyl vinyl ether, and cycloalkyl vinyl ether and / or alkyl vinyl ether as essential monomer components. The composition according to claim 1. 3. The copolymer (A) is obtained by copolymerizing fluoroolefin, hydroxyalkyl vinyl ether and vinyl carboxylate as essential monomer components. The composition according to item 1. 4. The copolymer (A) is obtained by copolymerizing fluoroolefin, hydroxyalkyl vinyl ether, vinyl carboxylate and cycloalkyl vinyl ether and / or alkyl vinyl ether as essential monomer components. A composition according to claim 1, characterized in that 5. The fluoroolefin is at least one selected from the group consisting of hexafluoropropylene, chlorotrifluoroethylene, tetrafluoroethylene, and vinylidene fluoride, and claims 2 to 4. Item 10. The composition according to any one of items.