JPS61217248A - General sheath material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to general exterior materials. For more information, see gloss,
This invention relates to a general exterior material having excellent weather resistance, antifouling properties, and corrosion resistance, being hard and scratch-resistant, and provided with a transparent protective layer.

[Conventional technology]

BACKGROUND ART Conventionally, a protective layer has been provided on a general exterior base material in order to impart corrosion resistance, rust prevention, antifouling properties, etc. to produce a ship exterior material. Such a protective layer needs to have excellent weather resistance, abrasion resistance, heat resistance, etc. as well as corrosion resistance, rust prevention, and stain resistance, as well as excellent durability.

Resins used for the above-mentioned 8WN include thermoplastic vinylidene fluoride resin, vinyl fluoride resin, acrylic resin, silicone resin, polyester resin, urethane resin, alkyd resin, vinyl chloride resin, phenol resin, epoxy resin, modified resins thereof, etc. , various paint resins have been developed and used.

[Problem that the invention seeks to solve]

The present invention is based on the findings that among conventionally used general exterior materials provided with Ml retention, there are very few that satisfy all of the above required performances, and only those that use thermoplastic vinylidene fluoride resin or vinyl fluoride resin are available. . However, when trying to form a protective layer using these resins, the
There are problems such as the need to bake at a high temperature of 300°C.

The object of the present invention is to provide a general exterior material that satisfies all of the above-mentioned performance requirements, is easy to construct, including repairs, and has a protective layer made of a resin that dries or hardens at room temperature. be.

[Means for solving problems]

The present invention relates to a general exterior material in which a protective layer mainly composed of a vinylidene fluoride copolymer having a functional group and/or a crosslinked product of a vinylidene fluoride copolymer having a functional group is provided on a general exterior base material. Regarding.

[Function and Examples]

The protective layer in the present invention is formed by applying a fluororesin paint consisting of a polymer composition containing a functional group-containing vinylidene fluoride copolymer (hereinafter referred to as a fluorine-containing copolymer) as a main component and a crosslinking agent, and applying the coating at room temperature. It is obtained by crosslinking and curing with a film thickness of about 5 to 100 μm.

The fluorine-containing copolymer has properties that conventional fluororesins do not have, namely, it cures at room temperature to form a hard film, and the formed coating film has the corrosion resistance, weather resistance, and antifouling properties of the fluoropolymer. It retains its characteristics such as It also has good adhesion to plastics, metals, wood, concrete, etc.

The components, composition, etc. of such a fluorine-containing copolymer are explained in detail in Japanese Patent Application No. 175123/1982.

In the present invention, the fluorine-containing copolymer usually contains 50 to 99 mol% vinylidene fluoride, preferably 65 to 85 mol%, and 1 to 50 mol% vinyl monomer having a functional group, preferably 1
~10 mol%, or 50 to 99 mol% vinylidene fluoride, preferably 65 to 85 mol%, 1 to 50 mol% vinyl monomers having functional groups, preferably 1 to 10 mol%, and fluoroolefins other than vinylidene fluoride. 30 mol%
It preferably consists of 10 to 25 mol%.

The molecular weight measured by gel permeation chromatography (GPC, polystyrene standard) of the fluorine-containing copolymer containing vinylidene fluoride as the main component and having a functional group is as follows:
Usually in the range of 10,000 to 500,000.

The vinyl monomer having the above-mentioned functional group usually has the formula: % formula %) (wherein,
represents an integer of 0 to 4 [1 to 4 when X is a hydroxyl group]. ), a compound represented by the formula: %formula%) (wherein, ~4 integer,
X is as above. ) A compound or a compound represented by the formula: %Formula% (wherein, Y is as defined above).

The fluoroolefins other than vinylidene fluoride mentioned above are usually tetrafluoroethylene, chlorotrifluoroethylene, monofluoroethylene, trifluoroethylene, hexafluoropropene, lower fluoroalkyl vinyl ether, etc., and preferably tetrafluoroethylene or chlorotrifluoroethylene. It is.

As a method for producing the fluorine-containing copolymer used in the present invention, for example, each component is mixed with a polymerization catalyst in the presence of a solvent at a temperature of -20 to 150°C, preferably 5 to 95°C, and
~30kg/cIl! G, preferably 10 kir/cJ
Methods such as emulsion polymerization, suspension polymerization, or solution polymerization in an aqueous medium under pressure conditions of G or less may be employed.

Furthermore, the fluorine-containing copolymer of the present invention has good compatibility with acrylic resins and can be used in combination with acrylic resins.

The above-mentioned acrylic resin refers to a single or copolymer of acrylate or methacrylate containing an alkyl group having 1 to 8 carbon atoms. For example, single or copolymers of methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl acrylate, copolymers of the above acrylates or methacrylates with hydroxyethyl methacrylate, methacrylic acid, glycidyl meccrylate, styrene, acrylonitrile, etc. Commercially available acrylic resins include Hyfroid 3004, Hifroid 3018, Hyfroid 3046C (all manufactured by Hitachi Chemical Co., Ltd.), Acridic A81.0-45, Acryzo Ink A314, Acridic 17-540 (
(all manufactured by Dainippon Ink and Chemicals), etc., but are not limited to these.

The acrylic resin preferably contains 50% by weight or more of methyl methacrylate and has a molecular weight (GPC) of 5,000 to 300,000 from the viewpoint of compatibility with the fluorine-containing copolymer.

The blending ratio of the fluorine-containing copolymer and acrylic resin is usually 1 part by weight of the fluorine-containing copolymer to 1 part by weight of the acrylic resin.
The amount is 0 to 1900 parts by weight, preferably 25 to 400 parts by weight. When blended within this range, the weather resistance, translucency, and
Good pigment dispersibility etc.

The protective layer in the present invention is usually prepared by blending a fluorine-containing copolymer with a crosslinking agent as described above, uniformly mixing and dissolving it in an appropriate solvent, and applying a coating composition to a general exterior base material.
It is formed by crosslinking and curing at room temperature. Curing progresses rapidly at room temperature, and a hard coating film is usually obtained within 1 to 10 days, but the time required for curing can be shortened by drying at a temperature raised to a level that does not adversely affect general exterior base materials.

A crosslinking agent is a compound having two or more groups capable of crosslinking the fluororesin by reacting with a functional group (hydroxyl group, carboxyl group, or glycidyl group) usually contained in the fluororesin. When the functional group is a carboxyl group, the crosslinking agent is usually isocyanates, amines, amino resins,
Compounds containing glycidyl groups, etc. When the functional group is a glycidyl group, it is usually an amine. Isocyanate 1-
Examples of the neck include, but are not limited to, hexamethylene diisocyanate, tolylene diisocyanate, hydrogenated tolylene diisocyanates, and block isocyanates thereof. Examples of amines include, but are not limited to, diethylenetriamine, triethylenetetramine, xylenediamine, metaphenylenediamine, penzyldimerylamine, bisaminopropyltetraoxaspiroundecane, and the like. Examples of acid anhydrides include phthalic anhydride, pyromellitic anhydride,
Examples include, but are not limited to, mellitic anhydride. Examples of amino resins include, but are not limited to, alkyl etherified methylol melamine, alkyl etherified methylol urea, alkyl etherified henzoylguanamine, and the like. An example of a compound containing a glycidyl group is the formula: %Formula% (wherein, Z represents a glycidyl group, and R1 represents an alkylene group having 2 to 10 carbon atoms or a divalent aromatic group having 6 to 10 carbon atoms. ), aromatic triepoxides represented by the formula; but not limited to.

The amount of the crosslinking agent is preferably adjusted to 0.5 to 2 equivalents based on all the functional groups in the fluorine-containing copolymer and the acrylic resin.

As the solvent, a wide variety of ordinary solvents can be used, unlike conventional fluorine-containing copolymers. Specific examples include esters such as ethyl acetate, butyl acetate, isobutyl acetate, and cellosolve acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cyclic ethers such as tetrahydrofuran; N-dimethylformamide, N-dimethylacetamide Examples include one or more of amides such as; alcohols such as methyl alcohol, ethyl alcohol, and butyl alcohol; and aromatic hydrocarbons such as toluene and xylene.

The concentration of the fluorine-containing copolymer varies depending on the coating method and coating manufacturing method, but is usually 5 to 70% by weight, preferably 20 to 60% by weight.

The fluorine-containing copolymer coating composition may optionally contain other polymers, curing accelerators, carbon black or titanium,
Inorganic pigments made of compounds such as zinc, lead, iron, etc., organic pigments, dyes, viscosity modifiers, leveling agents, anti-gelling agents, ultraviolet absorbers, light stabilizers, anti-scald agents, dispersants, antifoaming agents, etc. may be added. Examples of UV absorbers include:
Examples include salicylic acid derivatives, benzophenone compounds, hensitriazole compounds, and among these, benzophenone compounds are preferred. In addition, the amount used is 0 parts (parts by weight, hereinafter the same) per 100 parts (parts by weight, the same shall apply hereinafter) of the fluorine-containing copolymer or fluorine-containing copolymer and acrylic resin.
．． 01 to 10 parts, preferably 0.5 to 7 parts.

In addition, if necessary, other layers such as wash primer, anti-rust paint, epoxy resin paint, and other commonly used undercoat paints or other paints are provided on the general exterior base material, and the present invention is applied thereon. A protective layer may also be formed.

Application to a general exterior base material can be carried out by a conventional method such as a spray method, a brush coating method, a dipping method, a roll coating method, or a knife coating method.

General exterior base materials include metal-framed wall materials, panels, balconies, toys, window frames, curtain walls, gates, fences, shutters, roofing materials, and other home exterior materials, soundproof walls, road signs, guardrails, and outdoor materials. Examples include structures that are normally used outdoors, such as lights, signboards, and advertising towers, and can be made of metals such as steel, iron, aluminum, or alloys thereof.

Next, the general exterior material of the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.

Example I VdF 70%#%, CTFE 20 mol% and M5FP
50 parts (parts by weight,
The same applies below) was added to 50 parts of methyl isobutyl ketone and mixed uniformly, and then Coronate EH (polyisocyanate crosslinking agent manufactured by Nippon Polyurethane Industry ■) was added as a crosslinking agent to OHHI3 of the fluorine-containing copolymer and Coronate EH's N00 An amount equivalent to 1.1 and 0.05 g of dibutyl tin dilaure as a curing accelerator were added and mixed uniformly to prepare a coating composition.

A chemically treated steel plate (3308m plate made by Japan Test Panel Industry (11)) with a length of 150 mm, width of 70 mm, and thickness of 1 mm.
The coating composition was applied by brushing to give a film thickness of 27 μm.
A coating film was formed and cured at 25° C. for 7 days to form a protective layer.

Example 2 70 mol% VdF, 20 mol% CTFE and M5FP
Fluorine-containing copolymer consisting of IO mol% and MMA80
Acrylic resin consisting of mol%, HMAIO mol%, and HEMAIO mol% was mixed with methyl isobutyl ketone in a ratio of 70/30 (weight ratio) to prepare a 50% by weight varnish, and Coronate E H was added as a crosslinking agent.
For the OH value of 1 of the fluorine-containing copolymer and acrylic resin, an amount equivalent to 1.1 of the N00 value of EH and the curing accelerator dibutyl tin dilaurate were added uniformly in an amount of lXl0-'g per 1 g of solid content. were mixed to prepare a coating composition.

The above coating composition was applied to the same base material as in Example 1 and cured in the same manner as in Example 1 to form a protective layer with a thickness of 31 μm.

Comparative Example 1 An epoxy-melamine baking primer (primer for polyvinylidene fluoride made by Nippon Oil & Fats Co., Ltd.) was applied to the same chemically treated steel plate as in Example 1 by spray painting to give a 180%
C. for 6 minutes to form a coating film with a thickness of 7 μm. Furthermore, after spray painting polyvinylidene fluoride resin paint 2
It was baked at 50° C. for 10 minutes to form a protective layer with a total thickness of 32 μm.

Comparative Example 2 Methyl methacrylate 70 mol%, ethyl acrylate 20 mol% and hydroxyethyl methacrylate 10
A solution of toluene/butyl acetate-1/1 (weight ratio) containing 50% by weight of a copolymer consisting of mol% was prepared.

NGO content 12.5% for 150g of solution obtained
16 g (equivalency ratio: 1.0) of isocyanate (Japan Polyurethane side type Coronate HL) was added and mixed to prepare an acrylic urethane coating composition.

The coating composition was applied with a brush to the same chemical conversion treated steel plate as in Example 1, and cured at 25° C. for 7 days to form a protective layer with a thickness of 28 μm.

Comparative Example 3 Toluene/butyl acetate containing 60% of a copolymer consisting of 90% by mole of vinyl chloride and 10% by mole of vinyl acetate
A coating composition was prepared which was a 3/1 (weight ratio) solution.

The coating composition was barcoded onto the same chemical conversion treated steel plate as in Example 1, and dried at 20°C for 3 hours to form a protective layer with a thickness of 33 μm.

The following tests were conducted on the samples obtained in Examples 1-2 and Comparative Examples 1-3. The results are shown in Table 1.

[Light Sawa]

Measured using VG-2PD (glossy needle) manufactured by Hiki Denshoku Kogyo ■.

〔Weatherability〕

Using a Sunshine Weather-O-meter manufactured by Suga Test IA, an accelerated weather resistance test was conducted for 4,000 hours with continuous irradiation, a rain cycle of 18 minutes/120 minutes, humidity 60%, and a black panel temperature of 63°C, and the gloss retention rate was measured.

[Stain resistance]

After filling 1- on the test surface with Sakura Pentasochi (red) (manufactured by Sakura Crepas) and leaving it for 24 hours, wipe it with tissue paper impregnated with ethanol/methyl ethyl ketone (9/1 ratio) to remove any contamination. Visually check whether it is present. Note that in Table 1, ◯ indicates that it was completely removed, and × indicates that red color remained and could not be removed.

[Corrosion resistance]

Using a salt water spray tester manufactured by Suga Test S■, a 5% saline solution was sprayed onto the sample at 35°C for 2000 hours, and the appearance was determined.

Table 1 Examples 3 to 19 A fluorine-containing copolymer having the composition shown in Table 2 or a fluorine-containing copolymer and an acrylic resin (ratios shown in Table 2) were dissolved in methyl isobutyl ketone, and a solid Min concentration is 30
The weight percentage was adjusted accordingly.

Coronate EHO to the solid content of the solution OHHI3
An amount equivalent to NCO value 1.1 and dibutyltin dilaurate were added in an amount of 1X10-3 g per 1 g of solid content and thoroughly mixed, then applied with a brush to the same chemical conversion treated steel plate as in the example and cured at room temperature for 7 days. The cured coatings obtained were all glossy hard coatings with a thickness of about 28 to 33 μm.

Each sample was tested for weather resistance, stain resistance, and corrosion resistance. The results are shown in Table 2.

In addition, each abbreviation represents the following compound.

Vdp: Vinylidene fluoride CTFE: Chlorotrifluoroethylene TFE: Tetrafluoroethylene M5 FP: CFz=CFCF'gCHzOH3F
HA: CF'2”CFCH*CH20HHBVE
:Hydroxybutyl vinyl ether GVE nigericidyl vinyl ether 7 FHA: CFR=CFCF2CF, CH2CH
@OHMMA: Ethyl methacrylate EMA: Ethyl methacrylate HEMA: Hydroxyethyl methacrylate BMA Nibutyl methacrylate MA: Meccrylic acid GMA Nigericidyl methacrylate 5 F B A: CF 2 = CF CF 2
COOH (The following is a blank space, continued on the next page) [Effects of the invention] As described above, a polymer composition containing a functional group-containing vinylidene fluoride copolymer as a main component can be cured at room temperature, and has gloss and A protective layer with excellent weather resistance, antifouling properties, and corrosion resistance can be formed on a general exterior base coat. Therefore, the general exterior material of the present invention exhibits extremely excellent gloss, weather resistance, stain resistance, and corrosion resistance.

Claims (1)

[Claims] 1. Vinylidene fluoride copolymer having a functional group and/or
Or a general exterior material comprising a general exterior base material provided with a protective layer mainly composed of a crosslinked vinylidene fluoride copolymer having a functional group. 2. The general exterior material according to claim 1, wherein the protective layer contains an ultraviolet absorber.