JPS59189108A - Fluorine-containing copolymer and its composition - Google Patents

Abstract

PURPOSE:The titled room temperature-curable composition excellent in chemical resistance, weather resistance, and antifouling property, comprising a specified fluorine-containing copolymer and a functional group-containing methyl methacrylate copolymer. CONSTITUTION:A fluorine-containing copolymer is obtained by copolymerizing 40-60mol% chlorotrifluoroethylene with 25-50mol% 2,2,3,3-tetrafluoropropyl vinyl ether and 0.5-25mol% vinyl ether having a functional group selected from the group consisting of hydroxyl, glycidyl, and amino groups (e.g., hydroxylbutyl vinyl ether) at -20-150 deg.C and 0-30kg/cm<2>G in the presence of a polymerization catalyst in a solvent. This fluorine-containing copolymer is mixed with a functional group-containing methyl methacrylate copolymer (e.g., methyl methacrylate/hydroxyethyl methacrylate copolymer) at a weight ratio of 1/9-9/1 to obtain a composition which has a transmittance of at least 70% when measured with a 0.2mm.-thick cured molding thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable resin composition containing the copolymer and a methyl methacrylate copolymer having a functional group. More specifically, chlorotrifluoroethylene and 2.2,3
．． A copolymer consisting of 3-tetrafluoropropyl vinyl ether and a vinyl ether having a functional group (hereinafter referred to as the fluorine-containing copolymer of the present invention) and a methyl methacrylate copolymer having a functional group (hereinafter referred to as the fluorine-containing copolymer of the present invention) Sex MM
(referred to as A copolymer).

Fluororesin paints have excellent chemical resistance, weather resistance, stain resistance, heat resistance, etc., and are used in a variety of applications that take advantage of these properties. However, they usually have poor solubility in solvents and dissolve easily. In some cases, the types of solvents that can be used are limited, and furthermore, since these solvents have high boiling points, they have disadvantages such as the need for heat treatment at high temperatures in the coating machine. In order to eliminate the above-mentioned drawbacks, the combined use of methyl methacrylate polymers and fluorine-based polymers has been studied. However, to date, only vinylidene fluoride polymers have been found as fluoropolymers that can be homogeneously mixed with methyl methacrylate polymers and the like, excluding fluorine-containing methacrylate copolymers with low fluorine content. Generally, there are only a few types of solvents that can dissolve vinylidene fluoride polymers, and special solvents with high boiling points such as N,N-dimethylformamide and N,N-dimethylacetamide are required to dissolve them. Because it must be used, the drying temperature of the paint must be increased.

Paints containing vinylidene fluoride polymers and methyl methacrylate polymers have also been commercialized, but high-temperature baking is required to form films.

In recent years, research has been conducted on room-temperature-curing fluororesin paints that do not require baking at high temperatures. Studies have also been carried out to create room-temperature-curing fluororesin paints using copolymers with improved fluoride, but vinylidene fluoride has poor copolymerizability and requires the use of special fluorine-containing functional monomers. However, the current situation is that no copolymer that can be cured at room temperature has been developed.

Furthermore, copolymers consisting of fluoroolefin, cyclohexyl vinyl ether, and other copolymerizable monomer components have been proposed for the purpose of room-temperature-curing paints (JP-A-55-25414, JP-A-57-1999). No. 34107 and Japanese Unexamined Patent Publication Nos. 57-34108].

However, the above copolymer has a problem that it cannot be homogeneously mixed with methyl methacrylate polymer, which has good translucency.

In view of the above, the present inventors have conducted extensive research to create a fluorine-containing copolymer that can be used in fluorine-based room-temperature curing paints and can be homogeneously mixed with methyl methacrylate polymer. ethylene, 2,2,
3. The above objective can be achieved by a fluorine-containing copolymer consisting of one or more of 3-tetrafluoropropyl vinyl ether and a vinyl ether having a hydroxyl group, glycidyl group or amino group as a functional group (hereinafter referred to as functional vinyl ether). They have discovered that this can be achieved, and have completed the present invention.

That is, in the present invention, by selecting the above-mentioned specific fluorine-containing olefin compound as a component of the fluorine-containing copolymer, the copolymer can be produced by a normal polymerization method, and the resulting copolymer is composed of methyl methacrylate. It has been discovered that the polymer can be homogeneously mixed with or without a conventional solvent. The obtained copolymer can be used as a component of a paint to improve the chemical resistance, weather resistance, stain resistance, etc. of the paint. Furthermore, a composition containing this copolymer and a specific methyl methacrylate copolymer has room temperature curability, and has the remarkable effect that it can be used in paints and the like.

The functional vinyl ether used in the present invention has good copolymerizability with chlorotrifluoroethylene and 2,2°3,3-tetrafluoropropyl vinyl ether, and contains a functional group that can impart room-temperature curability. The one that does is used. Such functional vinyl ethers include vinyl ethers having a hydroxyl group, a glycidyl group, or an amino group, and specific examples include hydroxypropyl vinyl ether, hydroxyisopropyl vinyl ether, hydroxybutyl vinyl ether, hydroxy-2-methylbutyl vinyl ether, glycidyl vinyl ether, and ethylene. Oxyglycidyl vinyleminobi = /L/ x-thyl (0H2 = OHOCIH2
0H2NH2), propylamino vinyl ether, etc., and preferably hydroxybutyl vinyl ether, glycidyl vinyl ether, etc.

The proportions of chlorotrifluoroethylene, 2,2,3.3-tetrafluoropropyl vinyl ether and functional vinyl ether constituting the fluorine-containing copolymer of the present invention are 40 to 60 mol% of chlorotrifluoroethylene, 2, 2
, 3.3-tetrafluoropropyl vinyl ether 25
-50 mol%, functional vinyl ether 0.5-25 mol% is preferred. When the amount of chlorotrifluoroethylene exceeds 60 mol%, the solubility of the copolymer decreases, and when it becomes less than 40 mol%, the chemical resistance, weather resistance, stain resistance, etc. of the copolymer are reduced. properties deteriorate. When the amount of 2,2,3.3-tetrafluoropropyl vinyl ether exceeds 50 mol%, properties such as chemical resistance, weather resistance, and stain resistance decrease, and when it is less than 25 mol%, methyl methacrylate polymer It becomes difficult to mix homogeneously.

The amount of functional vinyl ether should be controlled in relation to hardness, chemical resistance, etc. according to the application, and if it exceeds 25 mol%, there will be problems with the solubility of the resulting copolymer due to the influence of the functional groups. If the amount is less than 0.5 mol %, room temperature curability cannot be improved.

The fluorine-containing copolymer of the present invention is produced by polymerizing chlorotrifluoroethylene, 2,2,3.3-tetrafluoropropyl vinyl ether, and a functional vinyl ether using a polymerization catalyst in the presence of a solvent at a temperature of 20 to 150°C. , preferably 5~
Produced by polymerization by methods such as emulsion polymerization, suspension polymerization, or solution polymerization in an aqueous medium at a temperature of 95 ° O and a pressure of 0 to 30 kf/am G, preferably 10 kf/am'' G or less. be done.

Examples of the solvent used in the solution polymerization reaction include trichlorotrifluoroethane, 1,1,1.2-tetrachloro-2,2-difluoroethane, methyl ethyl ketone, ethyl acetate, and butyl acetate.

Polymerization catalysts used in the above reaction include persulfates such as ammonium persulfate and potassium persulfate, sulfites of the above persulfates and potassium sulfite, sodium sulfite, and/or acids such as acidic potassium sulfite and acidic sodium sulfite. Redox polymerization initiators using sulfites, peroxide polymerization initiators such as diisopropyl peroxydicarbonate, t-butyl peroxybutyrate or benzoyl peroxide, and azo polymerization initiators such as azobisisobutyronitrile. Agents and the like are preferably used. The amount of the polymerization initiator used is usually 0.01 to 5% (wt%, the same applies hereinafter) based on the total amount of the monomers, preferably 0.
．． 05-1.0%.

The fluorine-containing copolymer of the present invention obtained by the above method includes methyl ethyl ketone, trichlorotrifluoroethane,
It can be homogeneously mixed by dissolving it in a solvent such as ethyl acetate or butyl acetate and mixing it with the methyl methacrylate polymer in a solution state, or by kneading it with heated rolls in the absence of a solvent. The curable resin composition of the present invention can be obtained by blending a functional MMA copolymer with the fluorine-containing copolymer thus obtained.

As the functional MMA copolymer used in the curable resin composition, a copolymer of methyl methacrylate and a monomer having a functional group such as hydroxyethyl methacrylate, glycidyl methacrylate, acrylamide, or methacrylamide is used. The functional MMA copolymer may optionally include ethyl methacrylate, butyl methacrylate, trifluoroethyl methacrylate, pentafluoropropyl methacrylate, methyl acrylate,
A third component such as butyl acrylate may be copolymerized and contained. The third component is used to adjust the homogeneity of the curable resin composition of the present invention or the film obtained therefrom, since it varies slightly depending on the type of functional group in the functional MMA copolymer.

The ratio of methyl methacrylate, the monomer having a functional group, and the third component in the functional MMA copolymer is 60 to 99.5 mol% of methyl methacrylate and 0.5 to 25 mol% of the monomer having a functional group. , the third component is 0 to 30 mol%. When the amount of methyl methacrylate is less than 60 mol%, the compatibility with the fluorine-containing copolymer of the present invention becomes poor,
A homogeneous mixture cannot be changed. If the amount of the monomer having a functional group exceeds 25 mol%, the compatibility with the fluorine-containing copolymer of the present invention deteriorates, and homogeneous mixing becomes impossible. The amount of functional groups in the resulting polymer decreases, making it impossible to obtain sufficient curability.

The weight ratio of the fluorine-containing copolymer and the functional MMA copolymer of the present invention is 179 to 9/1, preferably 3/1.
A range of 7 to 7/3 is desirable. When the number of functional MMA copolymers exceeds 90%, properties such as chemical resistance, weather resistance, and stain resistance, which are characteristics of fluorine-containing copolymers, are hardly obtained, and when it becomes less than 10%, Sensual MM
The characteristics of copolymer A, such as a high glass transition temperature, are reduced.

The curable resin composition of the present invention is cured by adding a curing agent. As a curing agent, when the functional group is a hydroxyl group, incyanates such as hexamethylene diisocyanate and its pentamers and derivatives, xylylene diisocyanate, tolylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated-4゜4′～
Diphenylmethane diincyanate and the like are used, depending on the purpose. When the functional group is a glycidyl group, amines such as diethylenetriamine, triethylenetetramine, xylene diamine, etc. can be used as curing agents.
Metaphenylenediamine, benzyldimethylamine, bisaminopropyltetraoxaspiroundecane, etc. are used, and they are used depending on the purpose. When the functional group is an amino group, linear diepoxides, aromatic diepoxides, aromatic triepoxides, etc., represented by the formula (4) may be used.

The curable resin composition of the present invention can be used as a paint or the like by dissolving or dispersing it in a solvent.

The paint prepared using the curable resin composition of the present invention can be used as an outdoor or indoor paint for metal, wood, concrete, plastic, etc., as well as a commercial paint, and has chemical resistance, weather resistance, and stain resistance. Excellent in sex etc. In particular, the coating film prepared from the curable resin composition of the present invention has a thickness of Q, 2
If it has a translucency of 70% or more in the wavelength range of visible light (mm), the clarity of the pigment added in the preparation of the paint and the gloss of the coating film will be good.

Next, the copolymers and compositions of the present invention will be explained with reference to Examples and Comparative Examples.

Example 1 350 g of ion-exchanged water and 1 g of sodium carbonate were charged into an iooo me glass autoclave, the space was sufficiently replaced with nitrogen gas to remove oxygen, and then 180 mj of trichlorotrifluoroethane was added. Prepare and then 2
,2. ! 1.3-tetrafluoropropyl vinyl ether 28.5y, hydroxybutyl vinyl ether 5.2
F and 28y of chlorotrifluoroethylene were charged. Heat to 45°0 with stirring and add diisopropylperoxydicarbonate as a polymerization initiator) 0.35.
was added and polymerized at the same temperature for 8 hours. The pressure at the start of polymerization was 2, Okf/am G, and the pressure after 8 hours of polymerization was 0.2 kg/am G. The polymer was dissolved in trichlorotrifluoroethane, and this was added to petroleum ether with stirring to reprecipitate it.

Thereafter, the polymer was dried under reduced pressure to obtain polymer 51f (83% polymerization rate).

The obtained polymer had a 35°0 teno intrinsic viscosity [77] +10.23 (d1/f) in methyl ethyl ketone, and a thermal decomposition temperature (in air, at which the weight loss started at an R temperature rate of 10°C for 7 minutes) at 277°C1. Differential scanning calorimetry (hereinafter referred to as DSO2)
Glass transition temperature measured using (heating rate 100o
7 minutes 2 was 43°0. Elemental analysis and infrared spectral analysis (hereinafter referred to as engineering R analysis) were performed on the purified polymer. The results of engineering R analysis confirmed that this polymer contains hydroxyl groups, and the results of elemental analysis showed that the molar ratio of chlorotrifluoroethylene/2,2,5.3~tetrafluoropropyl vinyl ether/hydroxybutyl vinyl ether was It was found to be a 5/4/1 copolymer of 8.

Elemental analysis value: Actual value f%): 031.7 Off 15.3
F43.8 Examples 2 to 5 Polymers having the compositions shown in Table 1 were prepared in the same manner as in Example 1. What? The amounts of chlorotrifluoroethylene used were all the same as in Example 1, and the amounts of other ingredients were varied as shown in Table 1.

The intrinsic viscosity, thermal decomposition temperature and glass transition temperature of the obtained polymer were measured in the same manner as in Example 1. The results are shown in Table 1.

Example 6 Methyl methacrylate in 300 mg 4 flasks) 4
6.8y, pentafluoropropyl methacrylate 6
f1 Hydroxyethyl methacrylate 7.2 Methyl ethyl ketone 60f as solvent, stearyl mercaptan as chain transfer agent 1. Oy$15 and azobisisobutyronitrile 0.51 as a polymerization initiator were charged. The inside of the flask was evacuated, heated to 70°0 with stirring, and polymerized at the same temperature for 7 hours, resulting in a viscous polymer solution (polymerization rate of 98%).

The intrinsic viscosity, glass transition temperature window and thermal decomposition temperature of the obtained polymer were measured in the same manner as in Example 1. The results are shown in Table 1.

The obtained polymer was subjected to engineering R analysis and elemental analysis. The results of engineering R analysis confirmed that this polymer contains hydroxyl groups, and the results of elemental analysis showed that it was methyl methacrylate/pentafluoropropyl methacrylate/
Hydroxyethyl methacrylate has a molar ratio of approximately 85
It turned out to be a 15/10 copolymer.

Example 7 Methyl methacrylate 69f1 glycidyl methacrylate 11f, methyl ethyl ketone 8
The polymer (
A polymer with a polymerization rate of 97.5% was prepared.

The intrinsic viscosity, glass transition temperature and thermal decomposition temperature of the obtained polymer were measured in the same manner as in Example 1. The results are shown in Table 1.

The obtained polymer was subjected to elemental analysis, and the results showed that the molar ratio of methyl methacrylate/glycidyl methacrylate was 90/10.

Example 8 In place of pentafluoropropyl methacrylate in Example 6, an equimolar amount of ethyl methacrylate was used for polymerization to obtain a polymer.

The intrinsic viscosity, glass transition temperature and thermal decomposition temperature of the obtained polymer were measured in the same manner as in Example 1. The results are shown in Table 1.

The polymer obtained from the analysis results is methyl methacrylate/
The molar ratio of ethyl methacrylate/hydroxyethyl methacrylate was approximately 80/10/10.

Examples 9 to 18 2 of the copolymers obtained in Examples 1.6 and 8, respectively.
A 0% methyl ethyl ketone solution was prepared and mixed in the proportions shown in Table 2, and homogeneous mixing was confirmed with the naked eye. 14 parts of hexamethylene diinocyanate trimer as a curing agent was added to 100 parts of the above mixture, mixed thoroughly, and then applied onto a sputter-etched tetrafluoroethylene/hexafluoropropylene copolymer film and cured at room temperature for 3 days. Thereafter, it was placed in a vacuum dryer to completely remove the solvent, yielding a coating film with a thickness fJ of 1 mm.

The light transmittance of the obtained coating film at a glass transition temperature of 2 and 650 parts m was measured in the same manner as in Example 1. The results are shown in Table 2.

Regarding the sample of Example 11, the transmittance of light of various wavelengths was also measured. The results are shown in Table 3.

The composition containing the curing agent is thoroughly degreased and has a thickness of 0.
．． It was applied onto a 2 mm aluminum plate, dried at room temperature for 3 days, and then placed in a vacuum dryer for 4 days to completely remove the solvent. Water, glycerin, diethylene glycol,
The contact angle was measured using methylene diiodide and tetrachlorethylene, and the critical surface tension was determined using a Zisman plot. The results are shown in Table 2.

Examples 19 to 21 The copolymers obtained in Examples 2 and 7 were made into 20% methyl ethyl ketone solutions and mixed in the proportions shown in Table 2, and homogeneous mixing was confirmed with the naked eye. 12 parts of bisaminopropyltetraoxaspiroundecane as a curing agent was added to 100 parts of the mixture and thoroughly mixed. Thereafter, a sample was prepared in the same manner as in Example 9, and the glass transition temperature, light transmittance, and critical surface tension were measured. The results are shown in Table 2.

The monograms of each copolymer in Table 1 are as follows.

0TFK: Chlorotrifluoroethylene 4FVK:
2,2,3.3-tetrafluoropropyl vinyl ether HBV]Ti: hydroxybutyl vinyl ether GV
K nigericidyl vinyl ether MMA: Methyl methacrylate 5PM: Pentafluoropropyl methacrylate HEMA: Hydroxymethyl methacrylate GMA
:' Glycidyl methacrylate EMA : Ethyl methacrylate Table 3 Example 22 and Comparative Examples 1 to 6 In place of the 2,2,3,3-tetrafluoropropyl vinyl ether used in Example 1, equal moles of the vinyl ether shown in Table 4 were added. A copolymer was obtained in the same manner as in Example 1 using the same amount.

The copolymer obtained in Example 1 and the copolymer obtained by the above polymerization were each made into a 20% methyl ethyl ketone solution, and the weight ratio of the 20% methyl ethyl ketone solution of the methyl methacrylate polymer shown in Table 4 was 171. 20 mj at a rate of ? The mixture was placed in a sample tube, capped and shaken, and then the compatibility was observed. The results are shown in Table 4.

In Table 4, O indicates that the mixed solution is homogeneous, Δ indicates that it is slightly non-uniform, and × indicates that the cloudy solution is separated into two layers.

Comparative Examples 7 to 8 A copolymer was prepared in the same manner as in Example 1 with a quaternary composition except that the i amount of 2,2,3,3-tetrafluoropropyl vinyl ether used in Example 1 was replaced with the vinyl ether shown in Table 4. I got it. Using the obtained copolymer, the compatibility with the methyl methacrylate polymer solution shown in Table 4 was measured in the same manner as in Example 22. The results are shown in Table 4.

The details of each vinyl ether in Table 4 are as follows.

8FVI: 0H2= 0H00H2(OF20F2
)2H16FV'E: 0H2= 0HOOH2
(CF'20F2) 4H Procedural Amendment (Spontaneous) September 20, 1980 Director-General of the Patent Office Kazuo Wakasugi Representation of Case 1 Patent Application No. 63599 of 1988 2 Name of Invention Fluorine-containing copolymer and Relationship with the case of the person making the composition 3 amendment Patent applicant address New Hankyu Building, 1-12-69 Kakita, Kita-ku, Osaka Name (285) Daikin Industries, Ltd. Representative Yama 1) Minoru) 1 5th supplement Subject of jF (1) Contents of Kusunoki 6 amendment of “Detailed Description of the Invention” of the specification (1) “1 ethylamino” in lines 4-5 on page 7 of the specification is changed to “
aminoethyl”.

(2) "1propylamino" on page 7, 1j' is corrected to "aminopropyl."

(3) Delete "in the presence of a solvent" on page 8, line 16.

(4) Correct [15,5J on page 15, line 20, to [15,5J].

(5) Add "50% solution of methyl ethyl ketone" next to "F mer" on page 19, line 1.

(6) Add "50% solution of methyl ethyl ketone" next to "n" on page 20, line 9.

Written amendment to the above procedure (voluntary) 5 November 28, 1980 Director General of the Patent Office Kazuo Wakasugi 1 Indication of the case 1982 Patent Application No. 63599 2 Name of the invention Fluorine-containing copolymer and composition thereof 3. Relationship with the case of the person making the amendment Patent applicant address 4@) H1-12-69, Kita-ku, Osaka City New Hankyu Building name (285) Daikin Industries, Ltd. Representative Yama I” Minoru 4 Agent 〒540 Amendment Contents of amendment (1) in the column ``Detailed Description of the Invention'' (σ) of the specification element].

(2) "Changes were made as shown in Table 1" on page 16, lines 5-6 were changed to obtain a copolymer having the composition shown in Table 1. 1 and correct it as 0. (3) Quantitative determination of 1-hydroxyl value (J
SK 0070-1966) and elements”.

(4) Correct “and” in line 2 of page 18 to “approximately”.

(5) "Analysis" on page 18, line 11 is corrected to "determination of hydroxyl value (according to J Eng SK 0070-1966) and elemental analysis".

that's all 45

Claims (1)

[Scope of Claims] 1. A fume containing one or more of chlorotrifluoroethylene, 2,2,3.3-tetrafluoropropyl vinyl ether, and vinyl ether having a hydroxyl group, a glycidyl group, or an amine 7 group as a functional group. Elementary copolymer. 2 40 to 60 mo/L' of chlorotrifluoroethylene
%, 2,2,3.3-tetrafluoropropyl vinyl ether in the range of 25 to 45 mol%, and the vinyl ether having the functional group in the range of 0.5 to 25 mol%. Polymer. 6 A fluorine-containing copolymer consisting of one or more types of chlorotrifluoroethylene, 2,2,3.3-tetrafluoropropyl vinyl ether, and a vinyl ether having a hydroxyl group, a glycidyl group, or an amino group as a functional group, and a functional A curable resin composition containing a methyl methacrylate copolymer having a group. 4. The composition according to claim 6, wherein the weight ratio of the fluorine-containing copolymer to the methyl methacrylate copolymer is 179 to 9/1. 5. The composition according to claim 1, wherein the molded article having a thickness of 0.2 mm after curing has a transparency of 70% or more to visible light.