JPS59127754A - Laminated structure having weatherproofing - 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 The present invention relates to a laminated structure having weather resistance, and more specifically, the present invention relates to a laminated structure having weather resistance. The present invention relates to a weather-resistant laminated structure provided with a coating layer made of a composition.

Conventionally, the mainstream of organic coated steel sheets has been colored galvanized iron sheets using thermosetting paint, but in recent years, steel sheets have been coated with vinyl chloride resin paste sol, or coated with vinyl chloride films or sheets. Vinyl chloride resin-coated steel sheets (hereinafter abbreviated as vinyl chloride steel sheets) laminated and bonded thereon have become widely used mainly because of their excellent design and corrosion resistance.

However, vinyl chloride resins inherently have poor weather resistance, and the plasticizers and stabilizers contained in vinyl chloride resins,
Because additives easily migrate to the surface of the film or sheet, the weather resistance of the PVC steel sheet itself deteriorates, resulting in significant discoloration and loss of gloss due to long-term outdoor use, and cracks in the PVC resin layer. may occur, resulting in a decrease in aesthetic appearance.
This had the disadvantage of causing a decline in corrosion protection.

As a method to eliminate such drawbacks, a method has conventionally been known in which the weather resistance of a PVC steel plate is improved by providing a coating layer of a resin composition with excellent weather resistance on the PVC steel plate. However, until now it has not only excellent weather resistance but also transparency,
No resin composition has been found that satisfies all the properties required for a coating material, such as flexibility, stress whitening resistance, water whitening resistance, solvent resistance, and processability, and cracks occur during bending. It may easily turn white due to impact or when exposed to hot water.
This caused various problems.

For example, polymethyl methacrylate is known as a resin with a beautiful appearance and excellent weather resistance, but because it is hard and brittle, it is not suitable as a material for the above-mentioned coatings. In resin compositions that attempt to improve the drawbacks by blending elastomer components or introducing an elastomer component through simple copolymerization, weather resistance.

Because various properties such as transparency and stress whitening resistance decrease,
None of these exhibits satisfactory properties as a coating material for PVC steel sheets.

For this reason, it has been desired to develop a coating material that does not have the above-mentioned drawbacks, and thereby to develop a laminated structure of PVC steel sheets with excellent properties.

An object of the present invention is to provide a laminated structure having extremely excellent weather resistance, solvent resistance, flexibility, processability, impact resistance, stress whitening resistance, water whitening resistance, and transparency.

The laminated structure of the present invention comprises a vinyl chloride resin-coated steel plate; and the following acrylic multilayer structure polymer [1251 to 99 layers,
and a coating layer formed of a resin composition comprising 1 to 49 parts by weight of a fluoropolymer [■], and the coating layer is formed on the vinyl chloride resin coating of the steel plate. It is characterized by

Acrylic multilayer structure polymer] (A) 60 to 100 parts by weight (hereinafter abbreviated as parts) of alkyl acrylate (AI) having an alkyl group having 8 or less carbon atoms, 0 to 40 parts of copolymerizable Monomers with heavy bonds (A
, ), 0 to 10 parts of polyfunctional monomer (A, ), and (AI)
- A polymer of 0.1 to 5 parts of grafting agent per 100 parts of the total amount of (A3), with a gel content of 60% by weight or more (hereinafter abbreviated as %) and a swelling degree of 50% Innermost layer polymer (5)) which is the following and accounts for 5 to 90 cX in the polymer [■]; ω) 60 to 100 parts of alkyl methacrylate (Bl
), and a monomer (B2) having 0 to 40 parts of a copolymerizable double bond, in which the amount in the polymer [1] is 1
An acrylic multilayer structure polymer in which 0 to 95% of the outermost layer polymer CB) is graft-bonded.

Fluoropolymer [■] The following formula: (In the formula, X and Y may be the same or different, and each represents I (, C1, F, CF) (b)
A homopolymer of vinyl monomer or vinylidene monomer represented by CH2,=C-C0ORH3 (in the formula, R represents a fluoroalkyl group), a copolymer consisting of two or more of these monomers, or a copolymer of two or more of these monomers, or a copolymer of two or more of these monomers. A copolymer containing 60 π or more by weight.

The present invention will be explained in more detail below.

The vinyl chloride steel plate used in the present invention is a steel plate covered with or laminated with a vinyl chloride resin, and may be produced by any method such as a paste-sol method, a sheet bonding method, or the like.

Next, the acrylic multilayer structure polymer CI used in the present invention
) will be explained in detail.

The innermost layer polymer (A) constituting the acrylic multilayer structure polymer [I] imparts flexibility and toughness to the polymer [■], and contains 60 to 100 parts of carbon atoms of 8 or less. Alkyl acrylate (At) having an alkyl group, 0-40
Part of monomer (A2) having a copolymerizable double bond, 0
~10 parts of polyfunctional monomer (A,) and (A,) ~(A
It is composed of 0.1 to 5 parts of graft cross-agent based on 100 parts of the total amount of 3).

Alkyl acrylate having an alkyl group having 8 or less carbon atoms
) (AI) may be linear or branched, and may include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, etc. alone or in combination. , preferably 80 to 100 parts, more preferably 90 to 100 parts. The lower the glass transition temperature (hereinafter abbreviated as T) of these materials, the more advantageous they are.

The monomer (A2) having a copolymerizable double bond is one that can be copolymerized with the alkyl acrylate (AI), such as lower alkyl methacrylate, lower alkoxy acrylate, cyanethyl acrylate, acrylamide, acrylic acid, and methacrylic acid. Preferred are acrylic monomers such as styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile, etc., which are used in an amount of 0 to 40 parts.

The polyfunctional monomer (A3) is used in an amount of 0 to 10 parts, specifically ethylene glycol dimethacrylate, propylene glycol dimethacrylate, and 1,3-butylene glycol dimethacrylate.

Alkylene glycol dimethacrylates such as 1.4 to butylene glycol dimethacrylate and propylene glycol dimethacrylate are preferred, and holyvinylbenzenes such as divinylbenzene and trivinylbenzene, alkylene glycol diacrylates, etc. can also be used. These monomers act effectively to crosslink the layers in which they are contained, but do not act on bonding between layers with other layers.

The grafting cross-agent is a combination of the above (AI) to (A,).

It is used in the range of 0.1 to 5 parts, preferably 0.5 to 2 parts per 100 parts, and specific examples include copolymerizable α, β-
Examples include allyl ester, meta-allyl ester, crotyl ester, hydrarylyl cyanurate, triallyl isocyanurate, etc. of unsaturated monocarboxylic acid or dicarboxylic acid. Examples of allyl esters include allyl esters such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid, with allyl methacrylate showing particularly excellent effects. If the amount of graft cross-agent used is less than 0.1 part, the effective amount for graft bonding is too small, and when the final polymer is molded, layer destruction will easily occur, resulting in a significant decrease in transparency, etc. . Moreover, if the amount exceeds 5 parts, the elasticity is particularly deteriorated, and sufficient flexibility and toughness cannot be imparted. In such a graft cross-agent, the conjugated unsaturated bond of the ester reacts much faster than the allyl group, methallyl group, or crotyl group, and is chemically bonded. During this time, a substantial portion of the allyl group, methallyl group, or crotyl group effectively acts on the polymerization of the next layer (in the next layer polymer) and provides a graft bond between the two adjacent layers.

The amount of the innermost layer polymer (A) in the acrylic multilayer structure polymer CD is 5 to 90%, preferably 10 to 70%, and can be set according to the required physical properties of the final resin composition. It is. If the amount of the innermost layer polymer (A) in the polymer [I] is less than 5%, the desired flexibility and toughness cannot be imparted to the acrylic multilayer structure polymer [11]. Further, if the amount exceeds 80%, the acrylic multilayer structure polymer [1] itself becomes rubbery and becomes difficult to handle, and various physical properties such as transparency are also significantly reduced. The innermost layer polymer (A) made of a crosslinked elastic body of acrylic rubber can have a two-stage structure or a three-stage structure, if necessary.

Furthermore, in addition to the above, the innermost layer polymer (A) has preferable ranges in terms of gel content, degree of swelling, particle size, etc. In particular, regarding gel content and degree of swelling, gel content is 60% or more, Preferably, the degree of swelling is 80% or more, and the degree of swelling is 50 or less, preferably in the range of 3 to 35. Note that the glass crystal temperature is preferably 0° C. or lower.

The particle size of the innermost layer polymer (A) is 500 to 500
If it is within the range of 0, the transparency and stress whitening resistance of the final multilayer structure polymer [I] will not be significantly reduced.

Next, the outermost layer polymer (B) constituting the acrylic multilayer structure polymer [I] is a resin component that imparts processability, weather resistance, solvent resistance, etc. to the polymer [I], and is therefore the most It is preferable that T of the outer layer polymer be higher, and preferable characteristics can be obtained when the temperature is 60° C. or higher. The layer (B) is 6
It is composed of 0 to 100 parts of alkyl methacrylate (B+) having an alkyl group having 4 or less carbon atoms and 0 to 40 parts of a monomer (B2) having a copolymerizable double bond.

As the alkyl methacrylate (BI) having an alkyl group having 4 or less carbon atoms, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc. are used, and among these, butyl methacrylate is the most preferred.

Examples of the monomer (B2) having a copolymerizable double bond include alkyl acrylates having an alkyl group having 8 or less carbon atoms, as well as those shown in the component (A2) above.

Outermost layer polymer (B) acrylic multilayer structure polymer [11
) is 10 to 95%. If the amount is less than 1O''X, a stable monomer cannot be obtained from the viewpoint of polymerization, coagulation, etc. If the amount exceeds 95%, the innermost layer polymer (A)
content becomes small, making it impossible to obtain the desired elasticity.

Incidentally, during the polymerization of the outermost layer polymer (B), it is possible to adjust the degree of polymerization by using a chain transfer agent, etc., and this is often preferable.

The acrylic multilayer structure polymer [1) used in the present invention has the above-mentioned innermost layer polymer (A) and outermost layer polymer (A) as basic structural units, but if necessary, the polymer ( Between the A) layer and the polymer layer, an alkyl methacrylate having 10 to 90 parts of an alkyl group having 4 or less carbon atoms (
CI), 10 to 90 parts of an alkyl acrylate (C2) having an alkyl group having 8 or less carbon atoms, 0 to 20 parts of a monomer (C3) having a copolymerizable double bond, 0 to 1 part of Polyfunctional monomers (C3) and (CI) to (C4)
(7) It is preferable to provide at least one intermediate layer (C) comprising 0.1 to 5 parts of a grafting agent based on 100 parts of the total amount. By disposing one or more intermediate layers having a composition intermediate between the innermost J@polymer (A) and the outermost layer polymer (B) and chemically bonding each layer with a graft cross-agent, resistance to damage can be achieved. It can be made to have excellent stress whitening properties. (CI) used here
Each component of (C3) and the grafting agent are the same as those of the polymer (
The same components as used in A) and (B) are used.

The amount occupied by the intermediate layer (C) in the acrylic multilayer structure polymer CD is usually 40% or less, preferably in the range of 10 to 35%.

Note that the gel content and degree of swelling of the innermost layer polymer refer to values measured as follows.

A predetermined amount of the polymer was collected in accordance with JIS K-6388, and methyl ethyl ketone (hereinafter referred to as MEK) was stored at 25°C for 48 hours.
It is abbreviated as ), immersed in it, swollen, and then pulled up to remove the attached M.
After wiping off the EK, its weight is measured, and then the MEK is removed by drying in a vacuum dryer, and the absolute dry weight, which has reached a constant weight, is calculated by reading and using the following equation.

Bone dry weight Also, the glass transition temperature (T2) refers to the value calculated by υ according to the following. In the formula, a+ and C2
each represents a weight fraction.

The multilayer structure polymer of the present invention is usually obtained by a sequential multistage polymerization method using an emulsion polymerization method. When the intermediate layer G) is multilayered, multistage polymerization may be carried out while gradually decreasing the amount of alkyl acrylate (Ct). When carrying out a sequential multi-stage polymerization method using emulsion polymerization method, a predetermined amount of an emulsifier, a catalyst, a monomer, etc. are added to an aqueous solvent and reacted, and after each reaction, the monomers and monomers forming the upper layer are added. By sequentially adding a polymerization initiator to the reaction system, the multilayer structure polymer of the present invention can be obtained.

There are no particular limitations on the emulsifier, catalyst, etc. used in the production of the multilayer structure polymer, and emulsifiers, catalysts, etc. used in ordinary emulsion polymerization can be used. As emulsifiers, long chain fatty acid salts, sulfonate salts, sulfosuccinic acid noester salts,
Typical examples include anionic surfactants such as phosphate ester salts and acid amide type anionic surfactants. Typical examples of catalysts include inorganic peroxides such as potassium persulfate, organic peroxides such as cumene hydroperoxide and lauroyl heroxide, and azo initiators such as azobisin butyronitrile. However, preferred examples include redox initiators such as cumene hydroperoxidium formaldehyde sulfoxylate.

The temperature conditions and polymerization time for the polymerization of the multilayer structure polymer depend on the catalyst used, etc., and any conditions are possible as long as the polymerization proceeds smoothly to the final stage. Usually, polymerization is carried out within a temperature range of 30 to 95°C, and the polymerization time is 3 to 20 hours. Note that it is often preferable to polymerize the crosslinked elastic body portion of the polymer at a relatively low temperature.

However, the method for producing polymer CD is not particularly limited to the above method; for example, after emulsion polymerization, the outermost layer polymer p)
When producing an emulsified multilayer structure polymer [■] which is converted to suspension polymerization during polymerization, there is no particular restriction on the emulsion particle size of the final polymer, but a range of about 800 to 2000A gives the most balanced structure. can get. There are no particular restrictions on the surfactants, catalysts, etc. used during production, and the latex of polymer [I] may be salted with additives such as antioxidants, lubricants, and coagulants as necessary. It is made into a powdery polymer by performing analysis treatment, followed by filtration, washing with water, dehydration, drying, etc.

What should be noted here is that when salting out using a metal salt, the residual metal content in the final polymer should be 500 ppm.
The following is extremely important and is one of the major features. In particular, when using metal salts with strong affinity for water, such as magnesium and sodium, as salting-out agents, the residual metal content must be kept as low as possible, otherwise whitening may occur when the final polymer is immersed in the water-saving solution. , which poses a big problem in practice. Naori lucium-based or sulfuric acid-based coagulation shows a relatively good tendency, but in any case, in order to provide excellent water whitening resistance, it is necessary to reduce the residual metal content to 500 ppm or less. The more the better.

Next, the fluoropolymer CD used in the present invention has the general formula CF2=CXY (X, Y= I(,F
.

Copolymers consisting of two or more of these monomers, or copolymers of these monomers and other copolymerizable monomers in which the ratio of these monomers is 60% by weight or more At least one kind of polymer selected from the group consisting of: Specific examples include polyvinylidene fluoride, polytetrafluoroethylene,
Polytrifluorochloroethylene, copolymer of tetrafluoroethylene and vinylidene fluoride, copolymer of tetrafluoroethylene and hexagonal propylene, poly(2,2.2-)rifluoroethyl methacrylate, etc. Typical examples thereof include polyvinylidene fluoride and copolymers of tetrafluoroethylene and vinylidene fluoride, which provide resin compositions with excellent properties.

Originally, this fluoropolymer (It) can be mixed with the acrylic multilayer structure polymer [■] in any ratio, but when used as a coating material, there are concerns regarding its adhesion to the base material. It is usually mixed in a range of 1 to 49% by weight.

Acrylic multilayer polymer [■] and fluoropolymer [1]
) Mixing can also be done by a normal method such as using a Henschel mixer, but it is preferable to heat both to a temperature above their softening point and mix them mechanically in that state. Methods such as passing through a screw type extruder that performs shear compression, mixing between heated rolls, or mixing in a heated high shear mixing device such as a Banbury mixer are used.

In the resin composition of the present invention, its weather resistance can be further improved by adding an ultraviolet absorber, and ordinary additives such as antioxidants and lubricants can also be added. Furthermore, by adding an appropriate amount of pigments, etc., the paper can be colored in any desired color, or once it has been formed on a film or sheet, it can be printed with various patterns by taking advantage of its excellent solvent resistance. It is possible to impart beauty to the laminated structure of the invention and further increase its added value.

If necessary, a matting agent may be added to the resin composition, especially a polymeric matting agent that causes less deterioration of physical properties (for example, JP-A-56-36
535, Japanese Patent Application No. 55-90149, etc.), the matte film or sheet obtained by laminating the matte film or sheet on a PVC steel plate, or the film of the resin composition having an embossed surface. By laminating the sheets, a laminated structure having a matte surface can also be obtained.

The resin composition of the present invention can be easily formed into films and sheets by conventional methods such as the T-Guy method, inflation method, and calendar method.

The laminated structure of the present invention has a coating layer made of a resin composition mainly composed of the multilayer structure polymer (1) and a fluoropolymer [1) described above, which is laminated on a vinyl chloride resin coating of a vinyl chloride steel plate. For example, (1) a method of bonding a film or sheet made of the resin composition under heat and pressure on a vinyl chloride resin coating of a vinyl chloride steel sheet; (2) chlorination of a vinyl chloride steel sheet. A method of applying an adhesive onto a vinyl resin coating and laminating a film or sheet made of the resin composition thereon; (3) a laminate obtained by coextruding the resin composition and a vinyl chloride resin; A method of attaching a film to a steel plate, (4) A film made of the resin composition and a vinyl chloride resin film are bonded under pressure under heat or laminated with an adhesive, and a laminated film is attached to a steel plate. Various methods can be used, such as (5) a method of directly providing a coating layer on a PVC steel plate while extruding the resin composition.

The laminated structure obtained in this way not only has excellent weather resistance, but also does not have the problem of cracking or whitening during bending, does not easily whiten due to stress or submersion, and has a good design. It has extremely high commercial value, with excellent properties such as solvent resistance, flexibility, processability, and transparency.

The present invention will be specifically explained below using Examples.

In the examples, all parts indicate parts by weight. In addition, the abbreviations used in the examples are as follows.

Methyl methacrylate MMA butyl acrylate) BuA2-ethylhexyl acrylate) ZEHA styrene
stl, 3-butylene dimethacrylate B
D allyl methacrylate) AMA cumene hydroperoxide CHP sodium formaldehyde sulfoxylate 5FSn-octyl mercaptan n-08H triallyl cyanurate TAC Example 1 Ions were placed in a reaction vessel equipped with a stirrer, a cooling tube, N, and a gas inlet. Prepare 250 parts of exchange water, 2 parts of ester salt of sulfoconophosphate, 6 parts of SFS o, o, and add N.
After stirring under two air streams to sufficiently replace the inside of the container with nitrogen, add 30 parts of BuA, 1 part of lumps, and 0.015 parts of C.
A mixture consisting of HP was charged, the temperature of the reaction system was raised to 40°C to initiate polymerization, and the reaction was continued for 180 minutes to complete the polymerization of the crosslinked elastic body (A) layer. The polymer (A) layer had a gel content of 93% and a swelling degree of 8. After the polymerization of the crosslinked elastic layer was completed, the temperature of the reaction system was raised to 80°C, and 0.07 parts of SFS dissolved in a small amount of water was added.
Part MAIO, 10 parts BuA, 15 parts AMAo, and 0.
A mixture of 0.2 parts of CHP was added over 60 minutes and held for an additional 60 minutes to polymerize intermediate J'@(C),
Next, 45 parts of MMA, 5 parts of BuA, n-08H0,0
A mixture of 25 parts and 0.05 parts of CHP was added over 60 minutes and held for an additional 60 minutes to complete polymerization of the outermost layer (B) to obtain a multilayer polymer latex. This latex was salted out using 5 parts of calcium chloride per 100 parts of the polymer, washed and dried to obtain a dry powder of the polymer. 90 parts of the polymer and polyvinylidene fluoride (Kynar 9
01, Pennwalt Co.) 10 parts and ultraviolet absorber 1.5
The mixture was mixed using a Henschel mixer, and then shaped into pellets using an extruder equipped with a screw having a diameter of 40 mm. After drying the pellets at 65° C. for a day and night, a film with a thickness of 50 μm was formed by an inflation method.

Layer this film on the PVC side of a PVC steel plate at a temperature of 190℃.
A laminated structure of the present invention was obtained by heat-compression bonding by passing between two rolls at a linear pressure of 2 Kf/'cj and a speed of 10 m/jth.

Bending test for this laminated structure (JISK67
44) and the DuPont impact whitening test (R=-1
noh, load IKf, and falling height 50 cIn), but no cracking, peeling, whitening, etc. were observed in any of the tests.

Also, commercially available PVC steel sheets showed significantly lower performance in accelerated exposure tests using a Sunshine Weather-Ometer (using WE L-HC model manufactured by Suga Test Instruments, black panel temperature 60°C, water spray 12-minute/60-minute cycle, exposure time 2000 hours). In contrast, the laminated structure of the present invention showed almost no change in appearance. As described above, it has been found that the weather resistance of the PVC steel sheet is significantly improved by coating it with the resin composition of the present invention.

Example 2 In the same manner as in Example 1, a multilayer structure polymer in which each layer had the composition shown below was obtained.

Crosslinked elastic layer (A) S BuA 30 parts, TACO, 1
5 parts middle layer (C) SBuA 5 parts, MMA 5 parts, TAC
O, 1 part outermost layer (resin layer) (B) 57 parts SMMA, Bu
A 3 parts (layer (A) gel content is 87%, swelling degree is 30) 80 parts of the polymer and tetrafluoroethylene-vinylidene fluoride copolymer (Kynar 7201, Pennwalt)
After mixing 20 parts of the mixture, 10 parts of a polymer matting agent (Metagren F410, Mitsubishi Rayon@), and 1.5 parts of an ultraviolet absorber using a Henschel mixer, the mixture was shaped into pellets using an extruder equipped with a screw having a diameter of 40 mm. After drying the pellets at 65° C. for a day and night, a matte film with a thickness of 50 μm was formed by the T-die method using the same extruder.

Next, after cleaning the surface of the PVC steel plate, apply a commercially available acrylic adhesive to a dry film thickness of about 5μ, and after thoroughly scattering the solvent, apply the above matte film. 10rn between two rolls with a linear pressure of 2 Ky/ctl
/Ith to obtain a laminated structure with a matte surface.

A bending test was performed on the obtained laminated structure, but no phenomena such as cracking or peeling were observed in the processed parts. Further, no change in appearance was observed in a 2000 hour accelerated exposure test using a sunshine weatherometer.

In this way, by coating with a matte film obtained from a composition that combines the resin composition of the present invention and a polymer matting agent, it has a calm matte appearance and has good processability and weather resistance. PVC steel sheets with excellent properties can be obtained.

Example 3 A multilayer structure polymer in which each layer had the composition shown below was obtained in the same manner as in Example 1.

Crosslinked elastic layer (A) 60 parts of HBuA, 0.6 parts of AMA Intermediate layer (C) 4 parts of S BuA, 6 parts of MMA, A
MA O, 075 parts Outermost layer (resin layer) (B)s MM
30 parts of A, 103 parts of n-08HO (gel content of layer (A) 90%, degree of swelling 10), 70 parts of the polymer, 30 parts of polyvinylidene fluoride, and 1.5 parts of ultraviolet absorber were mixed in a Henschel mixer, and the diameter It was shaped into pellets using an extruder with a 40+m screw. After drying the pellets at 60°C for a day and night, they were extruded into a film through a T-die using the same extruder, and a coating layer with a thickness of about 70 μm was directly formed on a PVC steel plate to form a laminated structure of the present invention. Obtained.

This laminated structure shows no cracking, peeling, whitening, etc. in the bending test and DuPont impact whitening test, and has excellent weather resistance.
No change in appearance was observed even after accelerated exposure after 00 hours.

Example 4 In the same manner as in Example 1, a multilayer structure polymer in which each layer had the composition shown below was obtained.

Crosslinked elastic layer (~: 22 parts of 2EHA, 2 parts of MMA, BD
1 part, AMAo, 2 parts middle layer (C,); 2EHA 7 parts, MMA 3 parts, AM
Ao, 1 part p (C,): 2EHA 3 parts,
7 parts MMA, 1 part outermost layer (resin layer):
5.5 parts of 2EHA, 49.5 parts of MMA (layer (A)
Gel content: 94%, degree of swelling: 5) 80 parts of the polymer and polyvinylidene fluoride (Kynar 901, Pennwalt)
20 parts and 1.5 parts of an ultraviolet absorber were mixed, and a 50 μm thick film was formed by the T-die method in the same manner as in Example 2. After back-printing a wood grain pattern on this film using a conventional method, this film was laminated onto a PVC steel plate in the same manner as in Example 2 to obtain a laminated structure with a beautiful wood grain pattern.

This laminated structure shows no cracking, peeling, whitening, etc. even in bending tests and DuPont impact tests, and has excellent weather resistance.
No change in appearance was observed even after 00 hours of accelerated exposure test.

Example 5 A multilayer structure polymer in which each layer had the composition shown below was obtained in the same manner as in Example 1.

Crosslinked elastic layer (A); BuA 27 parts, AN 3
part, TACO, 2 parts intermediate layer p); 5 parts of BuA, MMA
4 parts, St 1 part, TACO, 1 part Outermost layer (resin layer) (B); MMA 48 parts, 5t
12 parts (gel content of layer (A) 89%, degree of swelling 1.5)
90 parts of the polymer and polyvinylidene fluoride (Kynar 90
A laminated structure coated with the resin composition of the present invention was obtained in exactly the same manner as in Example 1 by blending 185 parts of a UV absorber and 185 parts of a UV absorber.

This laminated structure not only shows no cracking, peeling, or whitening in bending tests or DuPont impact tests, but also has excellent weather resistance, and even in 2000-hour accelerated exposure tests, it shows no cracks, peeling, or whitening. The above changes were not observed at all.

Claims (3)

[Claims] (1) A vinyl chloride resin-coated steel sheet; a coating formed from a resin composition consisting of 51 to 99 parts by weight of the following acrylic multilayer polymer [1] and 131 to 49 parts by weight of a fluoropolymer; A laminated structure having weather resistance, characterized in that the coating layer is formed on the vinyl chloride resin coating of the steel plate. Acrylic multilayer structure polymer [I] (A) 60 to 100 parts by weight (hereinafter abbreviated as parts)
Alkyl acrylate (At) having an alkyl group having 8 or less carbon atoms, 0 to 40 parts of a monomer having one copolymerizable double bond (
A2), 0 to 10 parts of a polyfunctional monomer (A3), and (A1) to
o, i to 5 parts of graft cross-agent based on 100 parts of total amount of (A,), a polymer having a gel content of 60% by weight or more (hereinafter abbreviated as %) and a swelling degree of 50% An innermost layer polymer (A) which is as follows and accounts for 5 to 90% in the polymer [■]; (B) having 6.0 to 100 parts of an alkyl group having 4 or less carbon atoms; Alkyl methacrylate (B, ), and 0-
40 parts of a monomer having a copolymerizable double bond (-B2
), in which the amount occupied in the polymer CD is 10
An acrylic multilayer structure polymer in which ~95% of the outermost layer polymer (B) is graft-bonded. Fluoropolymer [River] The following formula: (In the formula, X and Y may be the same or different and represent H, CL, F, OF, respectively.) (b)
CH2=C-GOOR l C■. (In the formula, R represents a fluoroalkyl group.) A homopolymer of a vinyl monomer or a vinylidene monomer represented by the formula (R represents a fluoroalkyl group), a copolymer consisting of two or more of these monomers, or a copolymer of two or more of these monomers, or a 60-layer mixture of these monomers. A copolymer containing the above. (2) In the acrylic multilayer structure polymer [4], the innermost layer polymer (A) and the outermost layer polymer) [1]
1) The amount occupied is 10 to 70% and 10 to 80%, respectively.
%, between the (A) layer and the CB) layer, C) 10 to 90 parts of alkyl methacrylate (C1) having an alkyl group having 4 or less carbon atoms, 10 to 90 parts of an alkyl group having 8 or less carbon atoms; Alkyl acrylate (C1) having an alkyl group, 0 to 20 parts of a monomer (C1) having a copolymerizable double bond
3), 0 to 10 parts of polyfunctional monomer (C4), and (C2) to
A polymer of 0.1 to 5 parts of a grafting agent based on the total amount of ioo parts of (C4), wherein the amount occupied in the polymer [■] is 1
Claim 1, wherein at least one or more intermediate layer 0 having a content of 0 to 40% is interposed by graft bonding.
A laminated structure having weather resistance as described in Section 1. (3) The weather-resistant laminated structure according to claim 1, wherein the fluorine-based polymer [ll] is polyvinylidene fluoride and/or tetra7tethylene-vinylidene fluoride copolymer.