JPH107866A - Vinylidene fluoride-based copolymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of giving coating film excellent in antiblocking effect, warm water resistance, hightemperature antifouling effect, finger touch dryability and abrasion resistance. SOLUTION: This composition comprises a vinylidene fluoride-based copolymer (VdF) and a thermoplastic acrylic polymer (TAP) 15×10<4> to 50×10<4> in weight-average molecular weight prepared by polymerizing monomers containing >90wt.% of methyl methacrylate in the weight ratio:TAP/VdF of (3:97) to (28:72).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinylidene fluoride copolymer composition. More specifically, the vinylidene fluoride copolymer composition of the present invention can be suitably used outdoors or indoors as a coating material for building materials and interior materials made of, for example, metals, resins, and inorganic base materials.

[0002]

2. Description of the Related Art There have been many proposals for coating a one-component fluororesin composition on, for example, building materials and interior materials to improve weather resistance and stain resistance. However, the thermoplastic acrylic resin blended as a binder in the one-pack type fluororesin composition generally has a low molecular weight, and the blending amount is small, so that the thermoplasticity of the resin as a whole is strong, The physical properties of the coating film underneath tend to fluctuate.

For example, when the objects to be coated are transported (for example, by car, train, ship or the like) in a high temperature atmosphere in summer, or stored in a warehouse, a container, or the like, the objects to be coated due to the softening of the coating film are formed. (So-called blocking) may occur.

In applications such as building materials, water resistance is often required as one of long-term durability, and when the resin in the coating film softens at a high temperature, the coating film becomes whitened by water absorption and shine. There is a problem that the commercial value is significantly reduced.

[0005] Further, due to the softening of the coating film surface, contamination from the outside is liable to occur, and it becomes difficult to remove it even by a washing treatment.

[0006] On the other hand, Japanese Patent Application Laid-Open No. 4-218538 discloses a coating with a highly durable two-component cross-linkable fluororesin. However, the resin is basically soft and can be sufficiently coated at high temperatures. Antifouling property cannot be obtained.

In addition, conventional fluororesin compositions do not provide abrasion resistance because of the use of a thermoplastic acrylic resin having a low molecular weight, and the compositions do not have sufficient quick-drying properties, so that they cannot be used after coating. No dryness to the touch is obtained.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a vinylidene fluoride copolymer capable of providing a coating film having excellent antiblocking properties, hot water resistance, high temperature antifouling property, dryness to touch and abrasion resistance. It is to provide a united composition.

[0009]

SUMMARY OF THE INVENTION The present invention provides a polymer obtained by polymerizing a monomer containing at least 90% by weight of a vinylidene fluoride copolymer and methyl methacrylate based on the weight of the monomer, and having a weight average molecular weight. A vinylidene fluoride-based copolymer composition containing 15 × 10 ⁴ to 50 × 10 ⁴ thermoplastic acrylic-based polymers, wherein the amount of the vinylidene fluoride-based copolymer is based on the amount of the thermoplastic acrylic-based polymer. 3 by weight
/ 97 to 28/72, which relates to a vinylidene fluoride copolymer composition.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The vinylidene fluoride copolymer composition of the present invention is most characterized by using a large amount of a high molecular weight thermoplastic acrylic polymer. Suppresses the degree of thermoplasticity of the components (ie, vinylidene fluoride copolymer and thermoplastic acrylic polymer), prevents softening of the coating, and has excellent blocking resistance, especially blocking resistance at high temperatures. Can be given.

The monomers used in the thermoplastic acrylic polymer that can be used in the present invention include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and (meth) acrylate. Esters such as butyl acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate or stearyl (meth) acrylate are exemplified. Of these, methyl methacrylate (methyl methacrylate)
Is an essential component and must be used as a monomer component of the acrylic polymer in a proportion of 90% by weight or more. If the proportion of methyl methacrylate is less than 90% by weight, the weather resistance, chemical resistance, compatibility between the resin components, hardness and chemical resistance of the coating film become insufficient. Preferably, it is a homopolymer of methyl methacrylate. The molecular weight of the thermoplastic acrylic polymer is preferably 15 × 1 in terms of polystyrene equivalent weight average molecular weight Mn (polystyrene equivalent by gel permeation chromatography).
0 ⁴ to 50 × 10 ⁴ , preferably 20 × 10 ⁴ to 2
It is 8 × 10 ⁴ . If the weight average molecular weight in terms of polystyrene is less than 15 × 10 ⁴ , the flexibility is poor, the bending resistance and the repetitive fatigue properties are poor, and sufficient anti-blocking properties cannot be obtained. If it exceeds 50 × 10 ⁴ , the viscosity is too high. ,
It is not preferable in the workability of coating.

In the present invention, the vinylidene fluoride-based copolymer has the weather resistance and chemical resistance inherent to a fluororesin,
This is for imparting water repellency and abrasion resistance to the composition of the present invention. Examples of the vinylidene fluoride-based copolymer include vinylidene fluoride (VdF), tetrafluoroethylene (TFE), and chlorotrifluoroethylene. (CTF
E), one or more copolymers obtained by copolymerizing two or more monomers among hexafluoropropylene (HFP), trifluoropropylene and the like. Particularly, among these, VdF / TFE copolymer, VdF / TFE / HFP copolymer, VdF / T
FE / CTFE copolymers and the like are preferable, and from the viewpoint of solubility in organic solvents, copolymers containing VdF units in an amount of 60 to 85 mol%, particularly 70 to 80 mol%, are preferable.
The weight average molecular weight of these copolymers is usually 3 × 10 ⁴
About 2 × 10 ⁵ .

The mixing ratio of the thermoplastic acrylic polymer and the vinylidene fluoride copolymer is such that the amount of the vinylidene fluoride copolymer to the amount of the thermoplastic acrylic polymer is 3/97 by weight. ~ 28/72 and 15/85
２７27/73. If the mixing ratio of the thermoplastic acrylic polymer is less than 72, it tends to soften, and it is difficult to obtain anti-blocking properties, hot water resistance, and high-temperature antifouling properties. The properties are impaired and the weather resistance is hardly obtained.

An organic solvent can be mixed in the vinylidene fluoride copolymer composition of the present invention. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, acetic acid and the like. Acetates such as butyl are preferable, and in addition, cellosolves, carbitols, aliphatic hydrocarbons, aromatic hydrocarbons such as toluene and xylene, alcohols, and chlorinated solvents are preferable.

The organic solvent used when the vinylidene fluoride copolymer composition of the present invention is applied to a plastic material such as polycarbonate is, for example, a ketone solvent having 3 to 6 carbon atoms, for example, Acetone, methyl ethyl ketone, diethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, cyclobutanone, cyclopentanone, methyl isobutyl ketone and the like can be mentioned, and methyl isobutyl ketone and methyl ethyl ketone are particularly preferred. When a ketone solvent having 3 to 6 carbon atoms is used in an amount of 10% by weight or more of the total solvent amount, the adhesion can be imparted by slightly dissolving the surface of the material. Examples of the organic solvent include other organic solvents such as methyl n-butyl ketone, ethyl n-butyl ketone, methyl n-amyl ketone, diisobutyl ketone, methyl n-hexyl ketone, mesityl oxide, cyclohexane, diacetone alcohol, methyl phenol ketone, Ketone solvents such as isophorone, ethyl acetate, n-propyl acetate, n-butyl acetate,
Ester solvents such as isobutyl acetate, 2-methoxyethyl acetate, amyl acetate, dimethyl adipate, dimethyl glutarate, dimethyl glutarate, dimethyl succinate, methyl cellosolve, 2-methoxy-2-propanol cellosolve, 1-ethoxy-2 -Ether solvents such as propanol butyl cellosolve, 1,4-dioxane, propylene glycol methyl ether, and propylene glycol methyl ether acetate can be used in combination. The proportion of the solvent in the vinylidene fluoride copolymer composition of the present invention is usually 95 to 60% by weight,
Preferably it is 85 to 75% by weight.

The solid content of the resin component in the vinylidene fluoride copolymer composition of the present invention is 5 to 40% by weight, preferably 15 to 25% by weight. 40
If the amount is more than 10% by weight, the viscosity of the vinylidene fluoride-based copolymer composition becomes too high, and the workability is impaired.

The vinylidene fluoride copolymer composition of the present invention may contain a heat stabilizer, an antioxidant, a lubricant,
Antifouling agent, ultraviolet absorber, light stabilizer, matting agent,
Paint additives such as dyes, defoamers, dispersants, and color pigments can be blended, and among these, it is particularly desirable to blend an ultraviolet absorber and a light stabilizer.

Examples of the ultraviolet absorber include benzophenone, benzotriazole, diphenylacrylonitrile derivatives (2,2-dihydroxy-4-methoxybenzophenone, ethyl-2-cyano-3,3-diphenylacrylate, 2-hydroxy-4- n-octoxybenzophenone, etc.) and a polymer type ultraviolet absorber ([2
-Hydroxy-4- (methacryloyloxyethoxy)
Benzophenone] / methyl methacrylate copolymer), and those containing 50% by weight or more of methyl methacrylate are preferred. These ultraviolet absorbers are resin components 1 in the vinylidene fluoride copolymer composition of the present invention.
It is preferably contained in an amount of about 1 to 12 parts by weight to 00 parts by weight.

Examples of the light stabilizer include nickel dibutyl dithiocarbamate, nickel bis (octylphenyl) sulfide, and [2,2'-thiobis (4
-Tert-octylphenolate)]-n-butylamine nickel, nickel complex-3,5-di-
tert-butyl-4-hydroxybenzyl, monoethylate phosphate, hindered amine type (bis (2,2,
6,6-tetramethyl-4-piperidyl) sebacate,
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 2- (3,5-di-t-butyl-4)
-Hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl) and the like, and these light stabilizers are It is preferably contained in an amount of about 0.1 to 10 parts by weight based on 100 parts by weight of the resin component in the polymer composition.

The coloring pigment is preferably contained in a proportion of 2 to 100 parts by weight based on 100 parts by weight of the resin component in the vinylidene fluoride copolymer composition of the present invention.

Other paint additives include, for example, silicone oils, silicone oligomers, fluorine oils, thickeners, antibacterial agents, fungicides, water and oil repellents, and fillers.

In addition, among the above-mentioned paint additives, those which are not used in a higher proportion are used in the resin component 1 in the vinylidene fluoride-based copolymer composition of the present invention.
It is preferably 0.05 to 5 parts by weight with respect to 00 parts by weight.

The vinylidene fluoride copolymer composition of the present invention can be produced by a conventional method. For example, the vinylidene fluoride copolymer, thermoplastic acrylic polymer, organic solvent, Accordingly, a method of mixing the paint additives at the mixing ratio described above may be used.

The coating method of the vinylidene fluoride-based copolymer composition of the present invention may be the same as the conventional coating method using a brush or a roller, spraying method such as air spray, airless spray, aerosol, dipping method, roll coating method. ,
Ink coating method can be adopted, for example, ceramics such as tile, cement, concrete, wood, metal,
It can be applied to polycarbonate resin, polyurethane resin, ABS resin, plastic such as FRP, rubber, and the like.

The obtained coating film is excellent in anti-blocking property, high-temperature antifouling property, hot water resistance and abrasion resistance, and further has coating workability (dryness to touch), recoating property, chemical resistance,
It is also excellent in weather resistance, such as tent cloth, marking film, wallpaper, housing equipment, building materials such as concrete panels and aluminum panels, automotive parts such as instrument panels, wipers, bumpers, table cloths, walls Suitable for interior materials such as seats and blinds.

The thickness of the coating film can be set according to the intended use, but is approximately 1 to 100 μm, preferably 3 to 30 μm.

[0027]

EXAMPLES Next, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

Examples 1 to 13 and Comparative Examples 1 to 12 (1) Production of vinylidene fluoride-based copolymer compositions Vinylidene fluoride-based copolymers were prepared so that the mixing ratios shown in Tables 1 and 2 were obtained. After weighing the thermoplastic acrylic polymer, these were mixed with ethyl acetate / toluene = 6/4.
(Weight ratio) in a mixed solvent, solid content concentration 26% by weight
The vinylidene fluoride copolymer composition was obtained.

This was diluted with a thinner of 4/3/3 (weight ratio) of methyl ethyl ketone / butyl acetate / toluene to a solid concentration of 10 to 15%, and further diluted with an ultraviolet absorber (Sumisorb, manufactured by Sumitomo Chemical Co., Ltd.). 130) was added as a coating material by adding 10% to the total amount of the resin.

These vinylidene fluoride copolymer compositions were applied to a chemical conversion aluminum plate and an ABS sheet to form test pieces, and various physical properties (2) to (5) described later were measured.

When applying to a chemical conversion aluminum plate, a white paint was applied in advance, and the vinylidene fluoride copolymer composition was clear-coated thereon (in the case of a chemical conversion aluminum plate, spray coating, ABS, etc.). In the case of the sheet, impregnation coating was performed, and the film thickness was about 20 μm by spraying and about 10 μm by impregnation coating). In addition, chemical aluminum plate, ABS
Both sheets are air dried and then dried at 150 ℃
For 5 minutes.

[0032]

[Table 1]

[0033]

[Table 2]

In Tables 1 and 2, VdF is vinylidene fluoride, TFE is ethylene tetrafluoride, Cd
TFE represents ethylene trifluoride chloride, and HFP represents propylene hexafluoride.

The weight-average molecular weights of the thermoplastic acryl-based polymers are all expressed in terms of polystyrene (measured by gel permeation chromatography). The vinylidene fluoride copolymer used had a weight average molecular weight of about 80,000 (in the same manner as described above, in terms of polystyrene).

The following vinylidene fluoride copolymer was used.

Examples 1 to 10: Zeffle LC-700 (manufactured by Daikin Industries, Ltd.) Examples 11 to 13: Kainer ADS (manufactured by Elf Atochem) The following thermoplastic acrylic polymers were used. .

Example 1: Dianal BR-82 (manufactured by Mitsubishi Rayon Co., Ltd., weight average molecular weight: about 15 × 10 ⁴ ) Examples 3, 6, 9 and 12: Dianal BR-85
(Mitsubishi Rayon Co., Ltd., weight average molecular weight about 26 × 10
⁴ ) Examples 4, 7, 10 and 13: Dianal BR-88
(Mitsubishi Rayon Co., Ltd., weight average molecular weight about 48 × 10
⁴ ) Examples 2, 5, 8 and 11: The above-mentioned DIANAL BR-8
2 (weight average molecular weight: about 15 × 10 ⁴ ) and the above-mentioned DIANAL BR-85 (weight average molecular weight: about 26 × 10 ⁴ ) were mixed and used at a predetermined weight ratio.

Comparative Examples 1-4: Dianal LR-630
(Mitsubishi Rayon Co., Ltd., weight average molecular weight about 4 × 1
0 ⁴⁾ Comparative Example 5-8: use in Examples 2, 5, 8 and 11: DIANAL BR-80 (Mitsubishi Rayon Co., Ltd., weight average molecular weight of about 9.5 × 10 ⁴⁾ Comparative Example 9-12 (2) Anti-blocking property at the time of laminating the ABS sheet Using the test pieces, the painted surfaces were overlapped, and after heating and curing under the conditions shown in Table 3, the following method was used. The sensory evaluation and the average peel strength were measured.

Sensory judgment: Judgment as "◎" when there is almost no tackiness due to finger touch, "O" when there is slight tackiness, and "X" when there is a clear tackiness and blocking. did.

Average peel strength: The cured sheet was peeled off using a tensile tester (Tensilon UCT-500 manufactured by Orientec Co., Ltd.) and the strength was measured. The conditions were as follows: test speed 50 (mm
/ Min), 2 kg full scale and 5 cm peel width.

Table 3 shows the results.

[0043]

[Table 3]

As is evident from the results in Table 3, when the vinylidene fluoride copolymer composition of the present invention was used (Examples 1 to 13), there was no stickiness even in the sensory evaluation, and the average peel strength was low. It is almost a fraction of Comparative Examples 1 to 8.

(3) Warm water resistance Using the test piece, the warm water resistance was visually observed under the conditions shown in Table 4, and when there was no abnormality, "◎" was marked, and the boundary with the slightly non-immersed portion was observed. Was evaluated as "O", when whitening and glossiness were conspicuous were rated "-x", and when whitening and glossiness were severe were evaluated as "x".

Table 4 shows the results.

[0047]

[Table 4]

As is evident from the results in Table 4, the appearance change when a general-purpose white paint is subbed on a chemical aluminum plate and the top clear coating is immersed in warm water shows that the total heat resistance of the resin is improved. Therefore, there is no water absorption whitening unlike the conventional product.

(4) High-temperature antifouling property A general-purpose white paint is undercoated on a chemical conversion aluminum plate, a vinylidene fluoride copolymer composition is top-clear-coated, carbon black is applied, and a heating treatment is performed at a predetermined temperature. After washing with water and observing the appearance visually, `` ◎ '' when the carbon black is completely removed, `` ○ '' when it is slightly remaining, and `` △ ~ × '' when it is slightly remaining. "," X "when the sample was clearly left, and" XX "when the sample was hardly removed.

Table 5 shows the results.

[0051]

[Table 5]

As is clear from the results shown in Table 5, the vinylidene fluoride copolymer composition of the present invention has a lower thermoplasticity than the conventional composition, so that the surface of the coating film is more heated. It is stable, hardly adheres to dirt from the outside, and has improved removability.

(5) Dryness to the touch, abrasion resistance and weather resistance Using the test piece (painted aluminum plate), a determination was made by the following method.

Dryness to the touch: Each of the above compositions was diluted with a thinner of MEK / butyl acetate / toluene = 4/3/3 (weight ratio) so that the resin solid content became 15%. And dried at room temperature (dry film thickness: approx.
m). Ten minutes later, the tackiness at the time of touching the finger is examined. When almost no tack is applied, “○” is selected, when slightly adhered, “△”, when slightly adhered, “△ to ×”, and when clearly adhered, “ × "
Was evaluated.

Abrasion resistance: ABS coated with each of the above compositions
Using a sheet, set it on a dyeing fastness tester for woven fabric and fiber material, and wear it for 2 minutes using a hard sponge scrubber as an attachment (load: 200 g, testing machine: dyeing fastness tester (Daiei Kagaku) )), “◎” when only slight scratches and good gloss are present, “、” when there are few scratches and gloss remains, and “△” when there are many scratches.
X ", and when there were many scratches and glossy," x "was evaluated.

Accelerated weathering tester: Performed under the conditions shown in Table 6 using the above-mentioned coated aluminum plate with an eye super UV tester W-13, and when there was no abnormality, it was evaluated as “◎”, and when there was faint gloss. “○”, and when there was a slight shine and evaluation, were evaluated as “○ to Δ”. Table 7 shows the results.

[0057]

[Table 6]

[0058]

[Table 7]

As is clear from the results in Table 7, Comparative Example 1
In Nos. To 8, the blended thermoplastic acrylic polymer has a low molecular weight and a small blended amount, so that the hardness of the coating film after coating is low, so that the quick-drying property is poor. Further, since the coating film strength is low, the coating film is easily damaged and has poor abrasion resistance.

However, in Examples 1 to 13 using the vinylidene fluoride copolymer composition of the present invention, the blended thermoplastic acrylic polymer has a high molecular weight, and the solvent release property of the resin as a whole is improved. Therefore, the quick-drying property after painting is improved. Further, since the coating film has a high strength, it is hardly damaged and the wear resistance is improved.

[0061]

As is evident from the above results, the vinylidene fluoride copolymer composition of the present invention has excellent antiblocking properties, especially at high temperatures, and is resistant to warm water and high-temperature antifouling. Gives a coating film with excellent properties, dryness to the touch and abrasion resistance.

Continued on the front page (72) Inventor Ryuji Iwakiri 1-1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (72) Inventor Susumu Wada 1-1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Inside the factory

Claims (2)

[Claims] 1. A polymer obtained by polymerizing a monomer containing 90% by weight or more of vinylidene fluoride-based copolymer and methyl methacrylate based on the weight of the monomer, and having a weight average molecular weight of 15
A vinylidene fluoride copolymer composition containing a thermoplastic acrylic polymer of × 10 ⁴ to 50 × 10 ⁴ , wherein the amount of the vinylidene fluoride copolymer is based on the amount of the thermoplastic acrylic polymer. Is a vinylidene fluoride copolymer composition in a weight ratio of 3/97 to 28/72. 2. The vinylidene fluoride-based copolymer is a vinylidene fluoride / tetrafluoroethylene copolymer, a vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer and a vinylidene fluoride / tetrafluoroethylene / chlorotriethylene copolymer. The vinylidene fluoride-based copolymer composition according to claim 1, wherein the copolymer is at least one of fluoroethylene copolymers and contains 60 to 85 mol% of vinylidene fluoride units.