JPS59204667A - Matte paint having excellent weather resistance - Google Patents

Abstract

PURPOSE:To obtain matte paint for the coating of the interior and exterior wall made of metal, concrete, slate, etc., and having excellent weather resistance, by adding a fluorine-containing matting agent to a specific fluorine-containing polymer soluble in a solvent. CONSTITUTION:The objective paint can be prepared e.g. by compounding (A) 100pts.wt. of a solvent-soluble fluorine-containing polymer having hardenable sites (e.g. one or more OH, epoxy group, carboxyl group, acid amide group, ester group, unsaturated bond, active hydrogen atom or halogen) and an intrinsic viscosity of 0.05-2.0dl/g measured in tetrahydrofuran at 30 deg.C, and composed of (i) 30-70mol% of a fluoroolefin, (ii) 70-30mol% of a vinyl ether and (iii) <=30mol% of a hydroxyalkyl vinyl ether or glycidyl vinyl ether and (B) 6- 100pts.wt. of a fluorine-containing matting agent (e.g. vinylidene fluoride).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a matte paint with excellent weather resistance, and particularly to a paint containing a novel fluorine-containing polymer to improve weather resistance.

When painting the interior and exterior walls of buildings made of metal, concrete, slate, etc., Zenzen paints are used for the purpose of enhancing the beauty of the walls and protecting them. Generally, only one fat with excellent weather resistance and light resistance is required to meet these purposes. Conventionally, examples of resins used in this type of paint include acrylic thread and acrylic-urethane.

A number of urethane-based resins have been proposed, and some of them are in practical use. However, these resins were not always fully satisfactory, especially in terms of weather resistance.

On the other hand, in recent years, these coatings have become popular with heavy and smooth tones, and matte tones have become popular instead of the traditional glossy tones. Conventionally, as such a matting agent, it has been proposed to mix fine inorganic powders such as silica and calcium carbonate into resin, or to add various kinds of fine organic powders such as epoxy resin, and some of them have not been put into practical use. has been transformed into However, although these generally have a smoothing effect, they inevitably have a negative effect on the smoothing properties of thick and small scratches (2h).

In view of these points, the present inventor has conducted various research and examinations with the aim of finding a paint that has a sufficient fade-out effect and has sufficient weather resistance, and has developed a specific fluorine-containing polymer. It has been found that the above object can be achieved by using the present invention.

Thus, the present invention has a cured site and an intrinsic viscosity of 0.05 to 2.0, measured at 30°C in tetrahydrofuran.
To provide a matte paint with excellent weather resistance, which is characterized in that a fluorine-containing matting agent is contained in a bath agent-soluble fluorine-containing coating composition eLl/17.

The fluorine-containing polymer used in the present invention must first have a curing site.

If there are no hardened areas, the coating will lack durability and be unsuitable when applied to the surface to be coated. The curing sites include hydroxyl groups,
Epoxy group, carboxyl group.

It is selected from acid amide groups, ester groups, unsaturated bonds, active hydrogen, and halogens, and must have at least one structure.

Also, if the intrinsic viscosity is too low, when applied to the surface to be painted,
If the mechanical strength is insufficient, and if it is too high, the concentration must be lowered due to viscosity, and solvent-insoluble ones are unsuitable because it becomes difficult to form a homogeneous coating. .

As the fluorine-containing polymer used in the present invention, addition polymer systems and condensation polymer systems can be used.

Examples of addition polymer systems include fluorine-containing unsaturated compound copolymers and copolymers of fluorine-containing unsaturated compounds, and condensation polymer systems include
Epoxies with fluorine-containing difunctional groups 111) Fats, or condensates of fluorine-containing/ols, dibasic acids, natural hydrates, diisonanate, etc., which form ester bonds, urethane bonds, mature leaf bonds, etc. is exemplified. As these fluorine-containing polymers, addition polymers such as copolymers of fluoroolefins and hydrocarbon vinyl ethers are preferable from the viewpoints of 1) durability, 2) mechanical strength, and releasability from the object to be coated. .

Fluoroolefins that can be suitably used in the present invention
The vinyl ether copolymer preferably contains 30 to 70 moles and 70 to 30 moles of moieties based on fluoroolefin and vinyl ether, respectively, and preferred fluoroolefin components include tetrafluoroolefin and chlorotrifluoroethylene. Also, preferable vinyl ether components include alkyl vinyl ethers 75 having linear bibranched or cyclic alkyl groups having 02 to C8.

In addition, as the comonomer that provides the curing site in such a copolymer, vinyl ethers containing functional groups such as hydroxy 7-alkyl vinyl ether or glycidyl vinyl ether are preferable. The above copolymers can be produced by reacting a monomer mixture in a predetermined proportion with a polymerization initiator or a polymerization initiation source such as ionizing radiation in the presence or absence of a polymerization medium to cause a copolymerization reaction. be.

A curing agent such as a polyfunctional compound that is reactive with the curing site of the fluorine-containing polymer used in the present invention is used in the polymer 10.
0.1 to 100 parts by weight, preferably 0 parts by weight
It is appropriate to mix it in a proportion of 5 to 50 parts.

Furthermore, in addition to this, a curing aid or curing catalyst may be appropriately blended. For example, for a fluorine-containing polymer whose curing site is a hydroxyl group, diisocyanate or titanium alkoxide can be preferably used as a curing agent when the fluorine-containing polymer is to be cured at room temperature. In addition, if the fluorine-containing polymer is to be heat-cured as desired, melamine curing agents, urea resin curing agents, polybasic acid curing agents, etc. used in ordinary heat-curing acrylic paints can be used for curing. It is effective as a drug. Here, the melamine curing agent includes butylated melamine,
Methylated melamine, epoxy-modified melamine, etc. are exemplified, and those having various degrees of modification from 0 to 6 can be used, and the degree of self-silkness can be selected as desired. Examples of urea resin and 1 to 1 include methylated urea, butylated urea, and the like.

Examples of the polybasic r/F curing agent include long-chain aliphatic dicarboxylic acids, aromatic polycarboxylic acids or their anhydrides, and block polyhydric cyaners (3X). When using a melamine or urea curing agent, curing can be accelerated by adding an acidic catalyst. Another example is amines when the curing site of the fluorine-containing polymer is an epoxy group.

Carboxylic acids, phenols, alcohols, etc. are effective as curing agents, and in this case, polyhydroxy compounds, especially non-aromatic diols, are useful as curing aids. It is desirable to select such a curing system appropriately depending on the type of substrate.

In the present invention, a fluorine-containing matting agent is contained in these fluorine-containing polymers. The fluorine-containing matting agent used is, for example, vinylidene fluoride.

Ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer, ethylene tetrafluoride-propylene hexafluoride copolymer, ethylene tetrafluoride-ethylene copolymer, ethylene chloride trifluoride-ethylene copolymer are appropriately employed. obtain.

The ratio of the fluorine-containing polymer to the fluorine-containing matting agent is preferably 100 for the former and 6 to 100 for the latter by weight.

If the usage ratio deviates from the above-mentioned range, it is not preferable because there is a possibility that the matting effect may not be obtained or the sustainability of the softening property may be reduced.

Furthermore, the paint according to the present invention may contain colored pigments such as titanium white and iron oxide, and essential pigments such as calcium carbonate.

Solvents such as xylene and toluene and other additives can be used in combination, and this is preferable in terms of cost and operation. When multiple components are used together in this way, the use of a fluorine-containing polymer or a fluorine-containing matting agent (1) is strictly determined by the type of the multiple components used, but in general, the use of a fluorine-containing polymer 20 ~50 j', j fabric%, fluorine-containing matting agent 3-20
It is practical to use a weight ratio of 2 to 25 weight ratios and a solvent volume of 30 to 50% by volume.

Next, the present invention will be explained with reference to examples.

Example 1 The molar ratio of chlorotrifluoroethylene, cyclohexyl vinyl ether, and hydroxybutyl vinyl ether is 50.40.10%, and the hydroxyl value is 50 fng
KOH, 7 g, 38% by weight fluorinated cumulative copolymer with an intrinsic viscosity of 0.23 al/F measured at 30°C in tetrahydrofuran, xylene/methyl isobutyl ketone 50%
150 mixed solvent 38]-'tl (%2 2% by weight of polymeric unsaturated polycarboxylic acid as a dispersant, 17% by weight of titanium white
, Tetrafluoroethylene-ethylene copolymer resin fine powder 5wt%
Furthermore, to 100 parts of these, 7 parts by weight of an incyanato curing agent were added and mixed uniformly. This was applied to an aluminum plate and the gloss by 6-fold specular reflection was measured. The cloth was 6o. there were.

Example 2 The molar ratio of chlorotrifluoroethylene, cyclohexyl vinyl ether, and glycidyl vinyl ether is 52
．． 27% by weight of a fluorine-containing polymer with an intrinsic viscosity of 0.19aA 7g measured at 30°C in tetrahydrofuran, 45% by weight of a xylene/methyl imbutyl ketone 5015 o mixed solvent, and as a dispersant. Add 2% by weight of polymeric unsaturated polycarboxylic acid, 11% by weight of iron oxide pigment, 15 parts of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin powder + A', and further add an incyanate curing agent to 100 parts of these. After adding 7 parts by weight and mixing uniformly, this was applied to an aluminum plate and the gloss was measured in the same manner as in Example 1.
Met. The invention of Example 1.2 was used as a commercially available acrylic resin paint.

Comparative acrylic/urethane resin paint (Nunyain type accelerated weathering test) (spray cycle 12 minutes/60
When an accelerated weathering test was conducted at a temperature of 60 degrees Celsius (black panel temperature: 60°C), deterioration such as chalking was observed with the acrylic resin paint after 750 hours and with the acrylic urethane resin paint after 1500 hours, but with the product of the present invention, deterioration such as chalking was observed after 2000 hours. No abnormalities were observed after use, and it was confirmed that not only did it have a matting effect, but it also had excellent weather resistance.

In addition, for the paint according to the present invention and the acrylic urethane resin paint, carbon black powder was placed on the painted surface, washed with water for 24 hours, and a contamination test was conducted to determine the degree of residual contamination. It was recognized that the stain resistance was low and the stain resistance was good.

Claims (1)

[Scope of Claims] 1. A solvent-soluble fluorine-containing polymer having a curing site and having an intrinsic viscosity of 0.05 to 2.0 dl/g when suppressed at 30°C in tetrahydrofuran. 1) A matte paint with excellent IM conditions, characterized by containing a matte agent. 2. The curing site is a hydroxyl group, an epoxy group, a carboxyl group,
Acid amide group, ester group, unsaturated bond, activated ice cream and...
- The paint according to claim (1), which is at least one selected from Rogen. 3. The fluorine-containing polymer is a copolymer of a fluoroolefin and a hydrocarbon vinyl ether, and the fluoroolefin and vinyl ether units each contain 30 to 7 units.
The paint according to claim 1, which contains units based on hydroxyal 4-ruhinyl ether or balcidyl vinyl ether in a proportion of 30 molar or less. 4 Fluorine-containing matting agents include vinylidene fluoride, ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer, ethylene tetrafluoride-propylene hexafluoride copolymer, ethylene tetrafluoride-ethylene copolymer, and trifluoride ethylene copolymer. The paint according to claim (1), which is an ethylene chloride-ethylene copolymer.