JPH02179743A - Composite sheet - Google Patents

Abstract

PURPOSE:To improve resistance to staining, by a method wherein a fluorine film is laminated to one side of a molding material consisting mainly of chlorinated vinyl chloride resin composition. CONSTITUTION:A fluorine film is laminated to one side of a molding material consisting mainly of chlorinated vinyl chloride resin composition. Chlorinated vinyl chloride resin whose chlorine content and specific viscosity are respectively about 60-72wt.% and at least about 0.20 is used for the chlorinated vinyl chloride resin composition. A rubbery substance such as MBS or ABS or CPE or NBR or multicomponent acrylic rubber resin or EVA or chlorinated polyethylene is used as an improver for shock resistance, in the chlorinated vinyl chloride resin composition. An ethylene-tetrafluoroethylene copolymer or an ethylene- chlorotrifluoroethylene copolymer or polyvinylidene fluoride or polyvinyl fluoride is mentioned as a fluorine resin molding a fluorine film. With this construction, a composite sheet superior in resistance to staining, resistance to whitening through water absorption, resistance to heat deformation and nonflammability can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides stain resistance, water absorption and whitening resistance.1. This invention relates to a composite board used for roofing and wall materials for sunrooms, car boards, etc., which has excellent heat deformation resistance, snow dusting resistance (snow accumulation prevention), weather resistance, and flame retardancy.

[Conventional technology]

Polycarbonate boards and acrylic resin boards are used for roofing and wall materials such as sunrooms and carboards used outdoors due to their weather resistance and 4# falcon resistance.

However, polycarbonate boards and acrylic resin boards have the disadvantage that sand, oil, etc. can easily accumulate on them, and the surfaces can become dirty easily.
In snowy regions, the drawback is that the snow is difficult to slide off. In particular, acrylic resin boards are flammable, which poses a problem in terms of fire protection, and they also have the disadvantage of having a heat softening temperature of 80°C or lower, making them susceptible to heat deformation in the summer.

On the other hand, boards made of Jllir, a chlorinated vinyl chloride tree, tend to absorb water and turn white, and they also tend to accumulate dust, oil, etc., and have poor stain resistance, so they are almost never used outdoors where they are exposed to wind and rain. .

[Problems to be solved by the invention]

The inventor has developed sunrooms and carports that have excellent stain resistance, water absorption and whitening resistance, heat deformation resistance, snow sliding resistance (snow accumulation prevention), weather resistance, and flame retardance, and are both practical and mobile. Since 7'JM, we have been conducting research to obtain roofing and wall materials for bus stops, platforms, guardhouses, etc., and have applied a fluorine-based film to at least one side of a molded material whose main component is a chlorinated vinyl chloride resin composition. The present invention was completed based on the discovery that by using a composite plate characterized by lamination, it is possible to form an excellent composite plate that solves all of the above problems.

[Means for solving problems]

The invention relates to a composite material characterized in that a fluorine-based film is deposited on at least one side of a molded material containing a chlorinated vinyl chloride-based resin composition as a main component of gold.

The present invention will be explained in detail below.

[Means to solve the problem]

The present invention provides a composite material characterized by laminating a fluorine-based film on at least one side of a molding material whose main component is a chlorinated vinyl chloride-based resin composition.
The target sound has been achieved.

The present invention will be explained in detail below.

First, the chlorinated vinyl chloride afB used in the chlorinated vinyl chloride resin composition that constitutes all of the present invention usually has a chlorine content of about 59 to 72% by gravity and a specific viscosity of 1f (JISK67
21 compliance) of about 0.20 or more, preferably those with a chlorine content of 62 to 68% and a specific viscosity of 0.20 to 0.60, more preferably a chlorine content of about 62 to 68%.
A material having an IE% of 65 weight and a specific viscosity of 0.30 to 0.50 is the ninth most suitable because it has excellent moldability and flame retardancy.

As a method for producing chlorinated vinyl chloride resin, for example, it is produced by chlorinating vinyl chloride resin powder in a gas phase, suspended in water, or in a solvent. For example, it is manufactured by the method described in Japanese Patent Publication No. 36-888.

Further, in the chlorinated vinyl chloride resin composition of the present invention, a blend of 100 parts by weight of chlorinated vinyl chloride resin to 100 parts by weight of vinyl chloride resin can also be used. As conventional compounding ingredients, various impact resistance improvers are used, for example, for the purpose of improving impact resistance.

For example, MBS (methyl methacrylate, butadiene-styrene copolymer), B8 (acrylonitrile-butadiene-styrene copolymer), cpg (chlorinated polyethylene), NBR (tolyl-butadiene rubber), multi-component acrylic rubber resin. , 87 (ethylene/acid picopolymer), chlorinated polyethylene, and other rubber-like materials are used, but CPE, BY, and multi-component acrylic rubber-based resins are particularly preferably used from the viewpoint of weather resistance. Furthermore, fibers such as glass fiber and asbestos are preferably used for the purpose of improving dimensional stability against environmental changes such as temperature. In addition, conventional compounding ingredients include various stabilizers such as tin-based and lead-based stabilizers, metal soaps, higher fatty acids, higher alcohols, lubricants such as amide waxes, antioxidants such as phenyl-α-naphthylamine, etc. -Ultraviolet absorbers such as dihydroxybenzophenone, coloring agents such as azo-threads, etc. can be used.

The saturation t1 of these compounding agents can be arbitrarily selected as long as the purpose of the present invention is not impaired.
Generally speaking, the impact resistance improver is 3ON'kk parts to 5 parts by weight, and the stabilizer is 0.5 parts by weight for a total of component (A) and component (B).
~7 parts by weight, Sui 4j 0.5 to 5 parts by weight, antioxidant 0 to 2 parts by weight, ultraviolet absorber θ to 5Xt parts, coloring agent 0 to 3 parts by weight, filler 0 to 5 parts by weight. It is selected in a range of 20 parts by weight.

The chlorinated cyclized vinyl resin composition used in the invention can be prepared by mixing the above-mentioned six combination components, for example, with a Henschel mixer, a Super Mixer, a Ribbon Blender, a Banbury Mixer-1? l
The mixture can be adjusted by putting it into a mixing area such as a crusher or mixing roll and mixing it uniformly at an appropriate temperature.

The thus prepared T-mixture is then passed through a molding machine such as a calender roll, a T-die extruder, or a press machine for 130 minutes.
A sheet or plate of required thickness is formed at a processing temperature of .degree. C. to 200.degree.

On the other hand, the fluorine-based film laminated on the molding material is molded using a fluorine-based resin.

Fluorine resin is a general term for added resins obtained by polymerizing olefins containing fluorine, and in general, the fluorine content is 451) or more, especially 50 polymers.
A number of k or more is preferably used. Examples of such fluororesins include ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, hexafluoropropylene-tetrafluoroethylene copolymer, and perfluoroalkyl vinyl ether-tetrafluoroethylene copolymer. Examples include ethylene copolymers, polyvinylidene fluoride, polyvinyl fluoride, etc., and any of these can be used in the present invention, but ethylene-tetrafluoroethylene copolymers are particularly preferred, and among them, The molar ratio of tetrafluoroethylene/ethylene is 40/60 to 60/40, and general 2〇Ha =
CHCnF'2n+x (however, n in the formula is 2 to 10
It is preferable that the perfluoroalkylvinyl monomer represented by (an integer of ) has a t'M amount of 0.1 to 10 mol.

The thickness of the fluorine-based film is preferably 5 to 500 μm
Particularly preferably, it is 10 to 200 an.

When a fluorine-based film is laminated on at least one side of a molding material having all the main components of a chlorinated vinyl chloride resin composition, it is generally preferable to laminate the fluorine-based film on the outside (the side exposed to sunlight). If necessary, fluorine-based films may be laminated on both sides.

In addition, when laminating fluorine-based films, it is preferable to perform lamination via an adhesive layer in order to improve adhesion.

Examples of the adhesive used at this time include acrylic adhesives, urethane adhesives, ethylene-vinyl acetate adhesives, etc. Acrylic adhesives are particularly preferred, but are not particularly limited. The acrylic resins used in the acrylic adhesive include ethyl acrylate, n-glopylacrylate, n-butyl acrylate, imbutyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. ,2
-Methyl butyl acrylate and the like.

Various additives and colorants can be added to the adhesive to improve weather resistance, heat resistance, and adhesion strength. Examples of these additives and colorants include the following ultraviolet absorbers, antioxidants, light stabilizers, tackifiers, plasticizers, and pigments/dyes.

UV absorbers: benzophenone, benzotriazole, cyanoacrylate antioxidants: phenol, phosphorus, sulfur light stabilizers: hindered phenol, Hindered amine tackifiers: Pinene, coumaron, petroleum hydrocarbon resin plasticizers: DOP and other pigments/dyes: lumps The above acrylic adhesives It is an adhesive composition comprising an adhesive resin component having a glass transition temperature of preferably 1100 to 50°C, a material having an ultraviolet absorption function, a material having a photooxidation prevention function, and gold, and is preferably applied to a load. The adhesive composition is such that the material having the ultraviolet absorption function is a benzo l-IJ azole external radiation absorber, and the material having the photooxidation prevention function is a hindered amine antioxidant.

In the case of the above-mentioned ultraviolet absorbers, benzotriazole-based ultraviolet absorbers are particularly suitable, and examples of the benzotriazole-based ultraviolet absorbers include 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole , 2-
(2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl)-2H-benzotriazole, 2
- (3,,5-di-t-amyl-2-hydroxyphenylbenzotriazole, etc.).

In addition, the amount of the material having the ultraviolet absorption function varies depending on the type and is not limited to horse chestnuts, but in order to fully demonstrate the performance of the material, the adhesive resin component (solid content) should be 100% by weight. It is preferably 0.5 to 103 parts, more preferably 0.6 to 2.5 parts.

Examples of the material having a photooxidation prevention function that can be applied to the present invention include hindered amine-based or hindered phenol-based antioxidants, among which hindered amine-based antioxidants are preferred.

The above-mentioned hindered amine-based antioxidant is not limited to 1%, but has a high molecular weight, N[
Preferable examples include those having a converted piperidizole nucleus.

The molecular weight of the above hindered amine antioxidant is as follows:
Preferably 400~io, ooo, 500~
5000 is more preferable.

As a specific compound of the above-mentioned hindered amine antioxidant, there can be mentioned a polymer ester which is an ester of butanetetracarboxylic acid and N-substituted piperiditul.・Manufactured by ADEKA ARGUS ■), MA KLA-62 (trade name, manufactured by ADEKA ARGUS@), etc. can be mentioned as preferable examples. By using a high molecular weight hindered amine antioxidant in this manner, bleed-out can be prevented, and as a result, performance can be maintained over a long period of time.

However, the amount of the material that exhibits the photooxidation prevention function varies depending on the type and is not particularly limited, but in order to fully demonstrate the performance of the material, the adhesive resin component ( It is preferably 0.1 to 5 parts by weight, more preferably 0.3 to 3 parts by weight, based on 100 parts by weight (solid content).

In this way, the sheet or board made of the chlorinated vinyl chloride resin composition and the fluororesin film are formed through the adhesive layer or directly using a roll, press, etc. to form the laminated board of the present invention. .

Next, Example t'' of the present invention will be specifically described.

Example 1 Chlorine content 1t (C1%) 65%, specific viscosity (ηsp) 0
．． 100 parts by weight of the chlorinated vinyl chloride resin No. 25, 4 parts by weight of EV (Evaflex EV250 manufactured by Mitsui DuPont Polychemicals), 1 part of CpE (Elastrene 351 manufactured by Showa Denko @) and a hinder amine type as impact modifiers. A chlorinated vinyl chloride resin composition containing 5 parts by weight of ultraviolet absorbers, organotin stabilizers, and lubricants such as wax and higher alcohol threads was used under roll cross-wire conditions at 170°C.
10 minutes, press molding condition 180℃ x 10 minutes, thickness 3 m
A transparent plate was molded.

Next, an ethylene-tetrafluoroethylene copolymer film (PETPH film) coated with an acrylic adhesive was pressed onto one side using a press to obtain a stacked board.

The PgTFE film used at this time was a 940μ film obtained by extrusion processing. The acrylate S adhesive used as the adhesive had a molar ratio of butyl acrylate and acrylic acid of 95:5, and had a weight average molecular weight of 500,000 violets and 100 parts by weight of the acrylic polymer.
In contrast, 2 parts by weight of 2-(3,5-, di-t-butyl-2-hydroxyphenyl)benzo l-IJ azole (ultraviolet absorber), hindered amine antioxidant (MARK
%LA-63, manufactured by Adeka Arthas ■ molecular weight 2060)
1! and 1:1 of ethyl acetate and toluene.
It was dissolved in a mixed bath medium to a concentration of about 40%. This acrylic resin solution was coated with an acrylic resin mixture so that the coating thickness after 3 minutes at 120° C. was 40 μm to obtain a PBTFE film V3-layer processed product. A laminate was obtained as described above.

The obtained laminate was used to evaluate various properties.

The results are shown in Table 1).

Example 2 Fluorex FLIR 2001 was used instead of the PETl'B film and acrylic adhesive used in Example 1.
) (manufactured by Rexham, adhesive-attached vinylidene film) was used in the same manner as in Example 1 to prepare a laminated sheet metal.

The results are shown in Table 1).

Example 3 The procedure was the same as in Example 1 except that Tetra-TUT 10AG3 (manufactured by DuPont, vinyl fluoride film, containing 25 μ% UV agent, no adhesive) was used instead of the PETFE film used in Example 1. A laminate was obtained.

The results are shown in Table II.

Comparative Example 1 Various properties were evaluated in the same manner as in Example 1 except that the PBTFE film was not bonded to a transparent plate made of a non-chlorinated vinyl chloride resin composition obtained in the same manner as in Example 1. It is described in Table-1.

Test method 1: According to the measuring device and measuring method specified in Heat Deformability STM D648, using a test piece prepared from a test plate of III (approx. 31), the temperature was raised under a load TM of 267-1b/Inx, 85℃
The depth of deformation was measured.

2. Surface stain resistance From a test board with a thickness of about 3 m1, 200 m in nine and 3000 m in width.
The test pieces were completely destroyed, exposed outdoors for one year at 45° on the P@ surface, measured the rate of decrease in surface gloss due to outdoor exposure using a digital variable angle gloss meter (Suga Test Instruments), and compared the stains. Completely complete.

3. Water Absorption Whitening A test piece of 200 tm long and 300 tm wide was taken from a test plate with a thickness of about 3H, and after immersing it in water at room temperature for one week, the state of whitening in the center of the test piece was compared with the naked eye. and evaluated according to the following prescribed criteria.

Judgment criteria: 0: Not much different from the original note.

1: Slight whitening is observed.

2: Significant whitening.

3: Completely changed to milky white.

4. Snow knife test From a test plate with a thickness of about 3 am, 2rn in 9, horizontal 1
Take each test piece of m and fix it outdoors on a 14g surface at a 20° slope during snowfall with no obstructions on the front, back, left and right sides of the test piece, and measure the deepest snow depth just before the snow slides down. (h) was measured to evaluate the ease of picking snow.

5. Oxygen index thickness: approx. 31) From the test plate of
A test piece of No. n was taken, and its oxygen index was completely measured according to the test method specified in JIS K6701, and the flammability was compared.

6. Combustibility A test piece of 60cm long and 150cm wide, taken from a test plate with a thickness of about 30mm, was fixed vertically and the flame of the burner was 5mm.
The state of smoke generation and the state of combustion were visually evaluated when the flame was brought into contact with the flame for a second and then removed.

7. Weather resistance test A test piece measuring 120 mm vertically and 60 mm horizontally was taken from a test plate with a thickness of 3 mm, and was subjected to a weather resistance test for 2000 hours using a Sunshine Weather-O-meter (manufactured by Toyo Rika Kogyo ■) with 1 trowel. went.

The transparency of the ¥f:, 1lII piece before and after the test was measured using a haze meter (manufactured by Toyo Seiki@), and the residual percentage of total transmittance was calculated by the following method.

For tensile strength, use a tensile tester (manufactured by Takasu Seisakusho).
The residual tensile strength was calculated.

〔Effect of the invention〕

As shown in Table II, the surface of the uninvented laminate is less likely to be soiled by dust and chips caused by wind, etc., there is only a slight decrease in gloss, there is no fear of thermal deformation even under stress in summer, and there is no risk of deformation due to rain. As a result, this FC laminate has excellent flame retardancy and does not cause any water absorption and whitening, and all nine defects found in conventional sunroom and car boat top materials have been improved, making this a product that should be loved by all. It turns out that.

Claims (5)

[Claims] (1) A composite plate characterized in that a fluorine-based film is laminated on at least one side of a molded material whose main component is a chlorinated vinyl chloride-based resin composition. (2) The composite board according to claim (1), wherein the composite board is laminated with an adhesive layer interposed therebetween. (3) The chlorinated vinyl chloride resin composition has a chlorine content (
Claim (1) characterized in that it contains a chlorinated vinyl chloride resin having a specific viscosity of 0.20 or more and a specific viscosity of 0.20 or more.
Composite board as described. (4) Claim characterized in that the chlorinated vinyl chloride resin composition contains 5 to 30 parts by weight of an impact modifier (
1) Composite board as described. (5) The composite board according to claim (4), wherein the impact resistance modifier is at least one impact resistance modifier selected from chlorinated polyethylene, ethylene-vinyl acetate resin, and multicomponent acrylic rubber resin.