JPS59215863A - Laminate - 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 laminate comprising a thermoplastic resin layer containing an aromatic vinyl compound and a vinyl cyanide compound and a polyvinylidene fluoride resin layer. A carcass (laminate) consisting of a resin composition layer consisting of a resin composition layer and a plastic resin layer containing an aromatic vinyl compound and a vinyl cyanide compound.

The thermoplastic resin containing an aromatic vinyl compound and a vinyl cyanide compound (hereinafter referred to as "thermoplastic resin") is styrene/acrylonitrile resin.

ABS resin, EPDM-styrene-acrylonitrile graft copolymer, etc. are widely known.

The common advantages of these resins are that they have excellent molding fluidity, that the surface of the molded product is beautiful, that they are relatively inexpensive, and because they are modified with rubber, ABS resins have excellent impact resistance. It is widely used for various purposes.

However, the common disadvantages of these resins are that they are flammable, are subject to severe deterioration due to ultraviolet rays, are easily abraded, have surfaces that are easily stained, and are susceptible to chemicals, which limits their use. The current situation is that

Various methods have been proposed to improve these shortcomings.

For example, a method of adding a flame retardant has been proposed in order to impart flame retardancy, but adding a flame retardant sacrifices the molding fluidity and aesthetic appearance of one-to-one resins, or sacrifices the appearance of impact-resistant resins. 9. In this case, the impact resistance will be significantly reduced. This would destroy the original advantages of thermoplastic resin. A method of adding urethane resin to improve the abrasion properties has also been proposed, but this causes the same problems as the addition of flame retardants mentioned above.

A method of increasing the amount of copolymerization of polar monomers such as acrylonitrile compounds has been proposed to improve chemical resistance, but even this method does not improve chemical resistance sufficiently and further deteriorates the processability of the resin. Moreover, it is not preferable because it reduces thermal stability and causes discoloration of the molded product.

At present, it is difficult to improve the common disadvantages of thermoplastic resins.

On the other hand, polyvinylidene heptadide resin has excellent molding fluidity and is excellent in weather resistance, chemical resistance, solvent resistance, abrasion resistance, heat resistance, flame retardance, etc., but it is expensive and is therefore widely used. It is a major hindrance to sexuality.

As a method to obtain molded products that have both advantages.

One possible method is to make a laminate of both.The styrene-based thermoplastic Mn resin molded product and the polyvinylidene sulfide resin do not have sufficient adhesion to each other.
The polyvinylidene fluoride resin peeled off, making it impossible to use this method in practice.

Therefore, the inventors conducted various studies on improving the interlayer adhesion between the thermoplastic resin molded layer and the polyvinylidene fluoride resin layer, and found that by mixing a specific acrylic resin with the polyvinylidene fluoride resin. The inventors discovered that the adhesiveness between polyvinylidene fluoride resin and thermoplastic resin was improved, and based on this knowledge, they completed the present invention.

That is, in the present invention, ethylenically unsaturated carbon L'[? Ester compound and fil that can be copolymerized with it if necessary
:Vinyl compound and Karagaru resin component 30-10
A composition consisting of an acrylic resin (A) and a polyvinylidene fluoride resin (B) whose main component is a polymer obtained by polymerizing l). Ritte (iy)
/' (B) A composition (C
) layer, an aromatic compound and a vinyl cyanide compound, and the content of vinyl cyanide itself in the resin component is 5 to 4.
The carcass is characterized in that it consists of a layer of thermoplastic resin (CD) having a weight of 0. The present invention will be explained in detail below. 1. Polyvinylidene fluoride resin (B) used in the present invention
is a resin containing not only a homopolymer of vinylidene heptadide but also a copolymer having a content of vinylidene heptadide of 90 moles or more.

As an ethylenically unsaturated carboxylic acid ester compound which is an essential component of the acrylic resin (4).

There are alkyl acrylates, algyl methacrylates, and esters of ethylenically unsaturated carboxylic acids and hydroxyalkyl, and examples of the alkyl acrylates include methyl acrylate.

Ethyl acrylate, etc. Examples of the argyl methacrylate 2 include methyl, methacrylate, and ethyl acrylate. The hydroxyalkyl ester of ethylenically unsaturated carboxylic acid (for example, β-hydroxyethyl acrylate, β-human tetraxyethyl methacrylate, etc.) is preferably an alkyl methacrylate, more preferably methyl methacrylate. be.

The content of the ethylenically unsaturated carboxylic acid ester in the resin component is not particularly limited, but is preferably 40 to 100% by weight, more preferably 60 to 100% by weight.

On the other hand, examples of the monomer copolymerized with the ethylenically unsaturated carboxylic acid ester include aromatic vinyl compounds, vinyl cyanide compounds, compounds having an amide group, and polyfunctional compounds, preferably hastyrene, α-methyl styrene,
There is acrylonitrile.

The acrylic resin (A) may be rubber-modified.

If a rubber-modified acrylic resin is used, a laminate with even better impact resistance can be obtained.

The rubbery polymer components used for this rubber modification include:
Diene rubbery polymers and non-diene rubbery polymers are used; diene rubbery polymers include polybutadiene, 8
BR, NBR, polyisoprene, polychloroprene, etc.

These rubbery polymers are made by emulsion polymerization, solution polymerization, etc., and include polybutadiene, polyisoprene, SBR, and styrene-butadiene block copolymers that are bonded with tin or lithium. These rubbery polymers can be used alone or in combination of two or more.

On the other hand, examples of non-diene rubbery polymers include ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, chlorinated polyethylene, normal butyl acrylate polymer, normal butyl acrylate and allylonitrile copolymer, and normal butyl acrylate. -butadiene copolymers, and acrylic rubber-like polymers such as n-butyl acrylate-butadiene-acrylonitrile copolymers. These non-diene rubbery polymers can be used alone or in combination of two or more.

It is also possible to use a mixture of a diene rubbery polymer and a non-diene rubbery polymer.

Preferred rubbery polymers include polybutadiene, SB
R, ]iiPDM, made of acrylic rubber.

E　P　D　M for applications requiring weather resistance.

Acrylic rubber is suitable.

The content of rubbery polymer (in the acrylic resin) is 70
If it is less than 70% by weight, it is 1 composition (C
) The content of the ethylenically unsaturated carboxylic acid nystere compound in the thermoplastic resin is low, and the adhesive strength with the thermoplastic resin (in the thermoplastic resin) decreases, making it impossible to obtain a laminate that can withstand practical use. It is not necessary to contain a rubber polymer, but the rubber content is preferably in the range of 5 to 40 degrees, more preferably 10 to I am in charge of the 30th grade.

The preferred flow value for acrylic resin) measured using a Koka type flow tester is Q, 5 to 40 (XIOCtd/”
sec, 200℃, aoKp/cA nozzle 1
×2m1m). For heavy use with acrylic Jugetsuji (A) and polyvinylidene fluoride Jurijima (B)
The compatibility with the laminate becomes better, and the surface condition of the aggregated laminate becomes beautiful.

Moreover, it is easy to obtain products with excellent mechanical strength.

There are no particular restrictions on the method for producing the acrylic resin of the present invention, including emulsion polymerization and suspension polymerization.

It can be suitably obtained by bulk suspension polymerization, bulk polymerization and solution polymerization.

Further, other resins such as AB8 resin and acrylonitrile-styrene copolymer may be appropriately mixed with the acrylic resin (A).

Acrylic resin (A) and polyvinylidene fluoride resin φ
The mixing ratio of ) is (A) 103) = 25~80/75~2
0 weight - acid, preferably (4)/(B) = 30-6
It is 0/70 to 40% by weight. If (B) is less than 20% by weight, the excellent performance of polyvinylidene fluoride cannot be maintained, and as a result, the laminate that is the object of the present invention cannot be obtained. On the other hand, if (B) exceeds 75% by weight, the adhesive strength with the thermoplastic resin (D) decreases, making it impossible to obtain a laminate that can withstand practical use. On the other hand, when Φ) is in the range of 40 to 70 weight -, a laminate with excellent adhesive strength and less deformation due to the difference in molding shrinkage rate between the molded products 03) and (C) can be obtained.

The content of the ethylenically unsaturated carboxylic acid ester compound in the composition (C) is at least 25% by weight, preferably at least 30% by weight, and more preferably at least 40% by weight. 25
If the weight is too high, the adhesive strength with the composition (C) laminated on the thermoplastic, grease-resistant CD will deteriorate, and it will not be used in practical use.
A laminate with a value of r1' cannot be obtained.

Thermoplastic resin 1 is a resin containing an aromatic vinyl compound and a vinyl cyanide compound. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, P, although it is not particularly controlled. There are methylstyrene, vinyltriene, and styrene containing nuclear chloride.

Among these, styrene and α-methylstyrene are preferred.

'/f Non-alcoholic vinyl compound [j Power is non-alcoholic vinyl thermoplastic: '+! 43. The content of the aromatic vinyl compound in the total weight is preferably 20% by weight or more, as it contributes favorably to the molding fluidity of item (D), and a product with good molding fluidity can be obtained when the process is less than 20%. Hateful.

Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile.

The amount of the vinyl cyanide compound is preferably 5 to 40% by weight, and more preferably 10 to 35% by weight, based on the total weight of the thermoplastic resin (b).

If it is less than 5% by weight, the adhesion between the polyvinylidene fluoride resin and the acrylic resin composition CG) will be weak and it will not be possible to obtain a laminate that can withstand practical use.On the other hand, if it exceeds 40% by weight, the thermoplastic resin (D) formability.

Thermal stability is reduced, the excellent properties inherent to the thermoplastic resin are impaired, and the industrial value is reduced.

In addition, monomers that can be copolymerized to the extent that the properties of the thermoplastic resin CD) are not impaired, such as vinyl compounds having an amide group,
N-methylol compounds, ethylenically unsaturated carboxylic acid esters, ethylenically unsaturated carboxylic acids, polyfunctional exomers, and the like can be used.

Examples of compounds having an amide group or N-methylol compounds include acrylamide.

Examples include methacrylamide and N-methylolacrylamide. As ethylenically unsaturated carboxylic acid compounds,
Acrylic acid, methacrylic acid.

7 malic acid, maleic acid and itaconic acid.

Examples include tyrenically unsaturated carboxylic acid Nisterbenzene A and the like.

The monomers can be used alone or in a mixture of two or more.

The fLH5 plastic resin (9) may or may not contain a rubbery polymer, but in applications where cut resistance is required, one containing a rubbery polymer is preferred.

As the gono-like polymer, the gono-like polymer mentioned earlier in the acrylic resin can be used.

What is the content of rubber-like monomer in the thermoplastic resin (J)?

If the amount is less than 40v, it will be removed, but if it exceeds 40% by weight.

hardness] (thermoplastic resin CD") is not suitable for use in fields where performance is required. From the viewpoint of balance between impact resistance and rigidity, the preferred range is 5 to 40% by weight. .

The method for producing the thermoplastic resin (D) is not particularly limited, but includes emulsion polymerization and suspension polymerization.

It can be obtained by bulk suspension polymerization, bulk polymerization and solution polymerization.

The thermoplastic resin (D) containing a rubbery polymer can be obtained by copolymerizing the monomer compounds described above in the presence of the rubbery polymer using the polymerization method described above.

Although the method of laminating the layer of the composition (C) consisting of the acrylic resin (4) of the present invention and the vinylidene fluoride resin (B) and the layer of the thermoplastic resin is not particularly limited, examples of the lamination method are not particularly limited. is shown below.

(1) A method of producing a laminate by drawing out (C) and (B) in a stacked state from a molding machine such as an extruder or a hot roll.

(2) A method in which the molded products of L (C) and (D) are formed using an extruder or a heated roll, and the sheets or films of C) and Φ) are stacked and bonded under heat.

(3) A method of stacking and compression molding the sheet of (C) and the pellet or powder of (B), or the sheet of (B) and the pellet or powder of (C).

(4) A method of dissolving (C) in a suitable solvent (e.g. dimethylformamide), applying this solution to the molded product of CD), and evaporating the solvent to obtain a laminate; A method of applying a dissolved solution to the sheet (C) and evaporating the solvent to obtain a laminate.

etc. can be implemented. These laminates are obtained by laminating another layer of (CD) or (C)) on at least one side of the molded product of (C) or Φ), and multiple layers of (C) and Φ) are laminated. It is also possible to determine the lamination surface according to the required performance in practical use. Further, the thickness of the laminate is not particularly limited, and can be arbitrarily provided depending on the application.

Typical uses of the laminate of the present invention include signboards that utilize the stain resistance of the polyvinylidene fluoride layer, materials for travel bags, and various signboards and road signs that utilize the excellent weather resistance of the polyvinylidene fluoride layer. Furthermore, since the polyvinylidene fluoride layer has strong resistance to various chemicals, it can also be used as storage containers for various chemicals.

1. Colorants, heat stabilizers, lubricants, and ultraviolet absorbers, if necessary, in the production of the laminate of the present invention.

It is also possible to add an antistatic agent or the like as appropriate.

Further, it is possible to suppress weather resistance deterioration of the laminate by adding a colorant having a strong light-hiding power such as titanium dioxide or carbon black to (C).

Furthermore, the layer of thermoplastic resin ('D) may be foamed.

The present invention will be explained in more detail below by referring to examples and comparative examples. Parts and sections on each side are by weight.

1. Acrylic resin (7) Acrylic resins having the compositions shown in Table 1 were used in the Examples and Comparative Examples.

2. As polyvinyritine fluoride (PUDF), Pennwalt's KYM A R740 was used.

3. Thermoplastic resin (G) Thermoplastic resin (D) having the composition shown in Table 2 was used in the Examples and Comparative Examples.

A laminate was evaluated using the following method using a combination of acrylic resin body shown in Examples and Comparative Examples P-3 and P-4), polyvinylidene fluoride resin (B) thermoplastic tt, and resin (D). .

(1" Preparation of molded product of composition (C) consisting of (A> and (PI) Use a 6-inch roll mixer to heat the object to 180℃.
After melting and kneading at ℃, use a press molding machine to
Pressure molded at 00℃.

A square Y plate having a side of 5 m and a thickness of 1 w was obtained.

The pellets were pressure-molded using a press molding machine at a temperature of 200°C to obtain a square plate of 5 cm on a side and 9 x 11 lr. (3) 7-layer method Carcass evaluation method (C) The molded product Φ and the molded product Φ) were stacked together and again pressure-molded using a press molding machine at a temperature of 200''C to obtain a laminated flat plate with a thickness of about 1.8 mm.

A strip-shaped test piece with a width of 1α and a length of 4 cm was cut out from this laminated flat plate, and the degree of adhesion was measured as shown below, and the deformation (warp) of the laminate was measured.
The condition was evaluated, and the surface condition and DuPont impact strength were evaluated using the flat plate itself as a test piece without being cut out.

1) Method for measuring the degree of adhesion of the laminated interface
111+Forcibly peeled off using a knife with a sharp edge.

Using Autoge 2 Hue S-2000 (registered trademark of a tensile testing machine manufactured by Rotsu Seisakusho), each peeled layer was grasped with an appropriate jig and tensed in vertically opposite directions to evaluate the degree of adhesion of the laminated interface.

2) Surface condition of laminate Visually inspect the surface condition of the composition (C) layer of the laminate.

Evaluation was performed based on the following criteria.

○ mark: surface smooth △〃〃〃：Slightly rough surface ×／／：　　It's rough. 3) Deformation (warp) state of laminate After molding the test piece, it was conditioned at 23°C for 8 hours.

The long side of the test piece on the composition (C) layer side of the laminate (4 cm)
The distance between the midpoint on the line connecting both ends of the sample and the surface of the test piece on the composition (C) layer side is measured (unit: m/m ).

The larger the interval, the greater the warpage, which is not desirable.

4) Method for Measuring DuPont Impact Strength The flat plate of the laminate was measured for falling weight impact strength using a DuPont falling weight impact tester at a temperature of 23°C.

In this measurement, the composition (C) layer was fixed so as to be on the upper side (the striking surface), and the striking rod used had a tip radius of 1 mm and 4 inches.

The evaluation results of each of the above examples and comparative examples are shown in Table-3゜-4.
It was shown to.

As shown in Table 3, the laminate according to the present invention fully achieves the object of the present invention.

On the other hand, in the comparative examples shown in Table 9-4, the laminates (A) and &e have low MMA content in (C) and cannot obtain sufficient adhesion, and furthermore, the laminates warp so much that they cannot be put to practical use. There are difficulties.

In the laminate (B), the amount of rubbery polymer in the acrylic resin (A) was outside the range of the present invention, and adhesion between the layers (C) and (D) could not be obtained.

In addition, in the case of the laminate (2), the amount of vinyl cyanide compound in the thermoplastic resin (D) was small, and close contact between the layer (C) and the scraps (D) could not be obtained.

Claims (1)

[Claims] A tree consisting of an ethylenically unsaturated carboxylic acid ester compound and, if necessary, a vinyl compound copolymerizable therewith, in the presence or absence of a rubbery polymer of 70 m1% or less. A composition comprising an acrylic resin whose main component is a polymer obtained by polymerizing 30 to 100% by weight of constituent components) and a polyvinylidene heptafluoride resin 03). (4)/CB)=25-80/75-20% by weight. A layer of the composition (C) in which the content of the ethylenically unsaturated carboxylic acid ester compound in the composition is 25% by weight or more, and a layer containing an aromatic compound and a vinyl cyanide compound, and a layer of the vinyl cyanide compound in the resin component. i with a content of 5 to 40% by weight
A laminate comprising a thermoplastic resin (D) layer.