JPS6241039A - Laminated structure - 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] [Industrial Application Field] The present invention relates to a laminated structure, and more specifically to a halogen atom-containing resin! ! ! (A) and at least two adhesive layers (B)
The present invention relates to a laminated structure consisting of layers, which maintains the excellent physical properties of a halogen atom-containing resin, which can be easily subjected to secondary processing such as heat-sealing and adhesion to other base materials, and which has strong adhesive strength.

[Prior Art] Halogen atom-containing resins, such as polyvinyl chloride (hereinafter simply referred to as PVC), have excellent versatility. Although it is a polymer and is widely used, it has the drawback of weak fusion properties. Therefore, various studies have been carried out on adhesives for these halogen atom-containing resins, and modified halogen atom-containing olefin polymers obtained by modifying halogen atom-containing olefin polymers with unsaturated carboxylic acids or derivatives thereof have been used for halogen atom-containing resins. It was discovered that it has a strong adhesive force. However, modified halogen atom-containing olefin polymers are polyolefins,
At present, it does not exhibit very strong adhesion to base materials such as metals, making it impossible to obtain a laminate.

[Problems to be Solved by the Invention] In view of the above-mentioned points, the present inventors have found that the halogen atom-containing resin can be easily applied to other base materials without impairing its excellent physical properties.
The object of the present invention is to provide a laminated structure that can be subjected to secondary processing such as heat fusion and adhesion, and has strong adhesive strength.

[Means for Solving the Problem] The present invention provides a halogen atom-containing resin layer (A) and an adhesive Jl.
In a laminate structure based on a laminate including at least two layers of (B), the adhesive layer (B) is obtained by modifying (I) a halogen atom-containing olefin polymer with an unsaturated carboxylic acid or a derivative thereof. Modified olefin polymer containing halogen atom 1 to 95% by weight, (II) Modified olefin polymer 99 obtained by modifying an olefin polymer with an unsaturated carboxylic acid or a derivative thereof
5% by weight of an adhesive resin or a composition containing the adhesive resin.

In the present invention, examples of the halogen atom-containing resin (A) used include polyvinyl chloride, polyvinylidene chloride, ethylene-vinyl chloride copolymer, chlorinated vinyl chloride resin, chlorinated polyethylene, chlorinated polypropylene, fluorine Examples include resins.

In the present invention, the olefin resin containing a halogen atom as the component (I) includes fluorinated olefin polymers, chlorinated olefin polymers, and chlorosulfonated olefin polymers, such as chlorinated polyethylene, Examples include chlorinated polypropylene, chlorosulfonated polyethylene, etc., especially those with a chlorine content of 5 to 60% by weight.
Chlorinated polyethylene is preferred.

Examples of the unsaturated carboxylic acids used in the component (I>) include monobasic acids and dibasic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, and citraconic acid. Derivatives of saturated carboxylic acids include these metal salts, amides, imides,
Examples include esters and anhydrides, and among these, maleic anhydride is most preferred.

The unsaturated carboxylic acid or its derivative (hereinafter simply referred to as unsaturated carboxylic acids) is 0.05 to 10 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the halogen atom-containing olefin polymer. and heated, preferably in the presence of an organic peroxide, to form a reaction. When the amount of unsaturated carboxylic acids added exceeds 10% by weight, decomposition and crosslinking reactions may occur in addition to the addition reaction, and when it is less than 0.05% by weight, the adhesiveness of the present invention is improved. cannot achieve that purpose.

Examples of organic peroxides include benzoyl peroxide, lauryl peroxide, azobisisobutyronitrile, dicumyl peroxide, [-butyl hydroperoxide, α,α'-bis(t-butylperoxydiisopropyl)] Benzene, di-t-butyl peroxide, 2,5-di(t-butylperoxy)hexyne, etc. are preferably used, and o, oos to 2,0 heavy chains are used per 100 parts by weight of the halogen atom-containing olefin polymer. Department,
It is preferably used in an amount of 0.01 to 1.0 parts by weight. If the amount of organic peroxide added is less than 0,00 parts by weight, the modification effect will not be substantially exhibited, and even if it is added in excess of 2,0 parts by weight, it will be difficult to obtain any further effect. At the same time, there is a risk that excessive decomposition or crosslinking reaction may occur.

The addition reaction of the unsaturated carboxylic acids mentioned above can be carried out by melt-mixing in an extruder or mixer such as a Banbury mixer in the absence of a solvent, or by reacting benzene, xylene, etc.
There are methods such as heating and mixing in a solvent such as aromatic hydrocarbons such as toluene, aliphatic hydrocarbons such as hexane, heptane, octane, etc., and the method is not particularly limited, but it is easy to operate, economical, etc. It is preferable to carry out the process in an extruder from the viewpoint of avoiding turbidity and continuity with subsequent processes.

The component (If) used in the present invention is an olefin copolymer modified with unsaturated carboxylic acids;
If) component olefin polymers include olefin homopolymers such as polyethylene, polypropylene, polybutene-1, and poly4-methyl-pentene-1, or ethylene, propylene, butene-1,4-methyl-pentene-1, etc. 1. Mutual copolymers of hexene-1, octene-1, etc., copolymers of ethylene and vinyl esters such as ethylene-vinyl acetate copolymers and their saponified products, ethylene-acrylic acid copolymers, ethylene-methacrylic Examples include copolymers of ethylene and unsaturated carboxylic acids, unsaturated carboxylic esters, etc., such as acid copolymers, ethylene-acrylic ester copolymers, ethylene-methacrylic ester copolymers, and mixtures thereof. Among these, ethylene polymers such as ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer are particularly preferred.

In addition, the unsaturated carboxylic acids in component (II) are (
Examples include the same unsaturated carboxylic acids described in the section regarding component I>, with maleic anhydride being particularly preferred.

The olefin polymer in component (II) is modified in the same manner as in the case of component (I) at the same mixing ratio. In addition, as another method for producing an adhesive composition comprising component (I>) and component (I), an adhesive composition comprising 1 to 95% by weight of a halogen atom-containing olefin polymer and 99 to 5% by weight of an olefin polymer can be used. Adding 0.05 to 10 parts by weight of unsaturated carboxylic acids to 10,012 parts of the mixture,
There is a method of carrying out thermal denaturation in the presence of 2.0 parts by weight of organic peroxide o, oos, and either Ilj production method may be used.

Component (I) and component (IF) are melt-mixed in an extruder or mixer such as a Banbury mixer, or mixed in powder or pellet form to obtain a modified halogenated polyolefin composition. (I) Ingredients and (I)
The mixing ratio with the components is (I) component containing m1 to 95% by weight;
(If) The content of the component is suitably in the range of 99 to 5% by weight. <I) When the content of the component exceeds 95% by weight,
Poor adhesion to base materials such as polyolefins and metals, and <
If the content of component I) is less than 1% by weight, the adhesion to halogen atom-containing resins such as PVC will be poor.

The laminate structure of the present invention is based on a laminate including at least two layers: a halogen atom-containing resin layer (A) and an adhesive layer (8). Other base materials that can be adhered through layer (B) include olefin polymers, polyamide resins, ethylene-vinyl acetate copolymers or saponified products thereof, polyester resins, polystyrene resins, ABS resins, and polycarbonate resins. resin, polyvinyl alcohol resin, polyphenylene oxide resin, polyphenylene sulfide resin,
Synthetic resins such as polyether/etherketone resin, polyethersulfone resin, polyamideimide resin, polyimide resin, polyacetal resin, polysulfone resin, boary arylate resin, polyetherimide resin, polyparabanic acid resin, or rubber, metal, FRP board ,wood,
Examples include glass, ceramic, concrete, plaster, woven fabric, non-woven fabric, paper, etc.

The laminated structure of the present invention has a halogen atom-containing resin layer (A)
The base is a laminate including at least two layers: and an adhesive layer (B), A/B, B/A/B1A/B/C (however, here, C is another layer of different material). ,A/B/C
/B, B/A/B/A1, C/B/A/B, C/B/A
This includes laminated structures of three, four, or five layers such as /B/C.

Methods for manufacturing the laminated structure of the present invention include compression molding, transfer molding, injection molding, extrusion molding, compressed air (vacuum)
Methods such as molding, press molding, and rolling are not particularly limited. For example, it can be manufactured by laminating a preformed polyvinyl chloride sheet, an adhesive sheet, and, if necessary, sheets of different materials, heating to a predetermined temperature, and rolling.

The form of the laminated structure of the present invention is film-like, sheet-like,
There are no particular limitations on the shape of a tube, plate, pipe, bottle, container, coated wire, injection molded product, etc.

[Operations and effects of the invention] The laminated structure of the invention has a halogen atom-containing resin layer (A)
and other base materials and an adhesive layer (B) that has strong adhesive strength.
A laminated structure consisting of at least two layers, which can be easily fused,
Secondary processing such as adhesion is possible.

As an example of actual use, taking advantage of the excellent weather resistance of polyvinyl chloride, a steel wire is coated with a polyvinyl chloride layer through an adhesive layer, such as in baseball fields, parks, parking lots, etc. It can be used for fence nets, cupboard nets, etc., and has far greater durability than conventional products made of polyvinyl chloride duplexes with steel wire inserted.

[Example J Hereinafter, the present invention will be specifically explained based on Examples and Comparative Examples.

1 to 6 and Comparative Examples 1 to 2 (Resin used) = Chlorinated polyethylene (chlorine content: 35% by weight, trade name: Daisolac G235, manufactured by Osaka Soda ■), anhydrous maleic [1G, 25% by weight] % and organic peroxide (product name: Verhexin 2,5B, manufactured by NOF Four Corporation)
50Imφ (screw diameter) with 0.02% by weight
Modified chlorinated polyethylene (hereinafter referred to as
(abbreviated simply as MCPE) was obtained.

■1; Modified ethylene-ethyl acrylate copolymer (containing ethyl acrylate ffl 20151%) modified with maleic anhydride (
Hereinafter, simply abbreviated as MEEA; Product name: 6 stones N Polymer A
1600, manufactured by Nippon Petrochemical Company).

■2: Ethylene-butene-1 copolymer (density 0.92
3 (1/ci, M I = 0.5+It/
Modified ethylene obtained by modifying (10 minutes) with maleic anhydride
Butene-1 copolymer is simply abbreviated as MLLDPE;
Product name: 6 stones N Polymer L 6030, Nippon Petrochemical ■
(manufactured by the company) was obtained.

A composition containing the above MCPE (I) and MEEA (II+) in the proportions shown in Table 1 was used as the adhesive (E3), and polyvinyl chloride resin (PVC; trade name) was used as the halogen atom-containing resin (A). Nearon': J'n Haunt BL 2M 11VI P, manufactured by Toagosei @ J Company)
They were preheated to 220°C and stacked on top of each other, and then pressurized at 100kg/d for 5 minutes in an oven at 220°C. After slow cooling, a test piece (25M width) was prepared, and a tensile speed of 50 was applied using a tensile machine.
Table 1 shows the adhesive strength measured by peeling at 180° at a*/min.

Also, for comparison, the above MCPE (I) and MEEA
(II+) was used alone and overlaid with PVC to measure the adhesive strength in the same manner as in Examples 1 to 6, and the results are also shown in Table 1 (Comparative Examples 1 to 2).

As shown in Table 1, MCPE (I) and MEEA
In Examples 1 to 6, in which (■1) was blended at a predetermined ratio, PV
Shows high adhesive strength to C. In contrast, MEEA
Comparative Example 2 using only (]I+) had low adhesive strength to PVC. Although Comparative Example 1 using only MCPE (I) has good adhesive strength to PVC, it has low adhesive strength to steel plates (hereinafter simply referred to as SUS) and is therefore not adopted in the present invention.

50 parts by weight of MCPE (I) of J22Kame Example 4 and MEEA (
I[+)50! Using the composition consisting of 5 parts as the adhesive (B) and ethylene-vinyl chloride copolymer as the other halogen atom-containing resin (A), 1300, manufactured by Nissan Kagaku ■ Co., Ltd.) and polyvinylidene chloride (hereinafter simply abbreviated as PVDC; manufactured by Gugo Kagaku ■ Co., Ltd.), the adhesive strength was evaluated in the same manner as in Example 1, and the results are shown in Table 2. .

Table 2 As shown in Table 2, an adhesive (
It can be seen that Sample No. 8) exhibits good adhesive strength with any of the halogen atom-containing resins (A).

Examples 9 to 11 The adhesive strength was evaluated in the same manner using the halogen atom-containing resins (A) of Example 4 and Examples 7 to 8, replacing (■1) in Example 4 with (I[2). The results are shown in Table 3.

Table 3 As shown in Table 3, an adhesive (B
) shows good adhesive strength with any of the halogen atom-containing resins (A).

11 and ≦l 50 parts by weight of MCPE (I) of Example 4 and MEEA (
III) Using 50 parts of the composition as adhesive (B), as another base material nylon-6 (hereinafter abbreviated as PA; trade name: Higashishi Amilan 1046, manufactured by Tsukushishi ■ Co., Ltd.) ,
Aluminum plate (hereinafter simply abbreviated as Aj), high-density polyethylene (hereinafter simply abbreviated as IDPE; density 0.94)
6 g/d, M I = 0.05 g/10 min, product name: Nippon Seki Stafrene E905, manufactured by Nippon Petrochemical Co., Ltd.), steel plate (SUS
(abbreviated as: 5PCG-8D) and polyethylene terephthalate (hereinafter simply abbreviated as PEr; trade name: Kodar
The adhesive strength was measured in the same manner as in Example 4 using PET G 6763, a product of Eastman Chemical Products Inc., and the results are shown in Table 4.

Table 4 As shown in Table 4, the adhesive (B) consisting of 50 parts by weight of MCPE (I) and 50 parts by weight of MEEA (M + ) exhibited good adhesive strength with both base materials. I understand.

Friend 1” YuLjil Replace (I[+) with (■2) in Examples 12 to 16,
The adhesive strength was similarly evaluated and the results are shown in Table 5.

Table 5 As shown in Table 5, it can be seen that the adhesive (B) consisting of 50 parts by weight of MCPE (I) and 50 parts by weight of MLLDPE (II2) exhibits good adhesive strength with both substrates.

Claims (1)

[Claims] 1. A laminate structure based on a laminate including at least two layers: a halogen atom-containing resin layer (A) and an adhesive layer (B), wherein the adhesive layer (B) is ( I) 1 to 95% by weight of a modified halogen atom-containing olefin polymer obtained by modifying a halogen atom-containing olefin polymer with an unsaturated carboxylic acid or its derivative, (II) a modified olefin polymer obtained by modifying an olefin polymer containing a halogen atom with an unsaturated carboxylic acid or its derivative. Modified modified olefin polymer 99~
5% by weight of an adhesive resin or a composition containing the adhesive resin. 2. Claim 14, wherein the halogen atom-containing resin (A) is at least one selected from the group of polyvinyl chloride resins, polyvinylidene chloride resins, chlorinated polyolefin resins, and fluorine resins. Laminated structure. 3. The laminate structure according to claim 1, wherein the component (I) is modified chlorinated polyethylene obtained by modifying chlorinated polyethylene with maleic anhydride. 4. The modified chlorinated polyethylene contains 0.05 to 10 parts of maleic anhydride per 100 parts by weight of the chlorinated polyethylene.
4. The laminated structure according to claim 3, which is added in parts by weight and heat-denatured in the presence of an organic peroxide. 5. The laminate structure according to claim 3 or 4, wherein the chlorine content of the chlorinated polyethylene is 5 to 60% by weight. 6. The olefin polymer of component (II) is selected from the group of ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer. The laminated structure according to claim 1, which is at least one type of. 7. The laminate structure according to claim 1, wherein the unsaturated carboxylic acid or its derivative as component (II) is maleic anhydride. 8. The component (II) is 0.05 to 10 parts by weight of maleic anhydride added to 100 parts by weight of the olefin polymer;
The laminate structure according to claim 7, which is thermally denatured in the presence of an organic peroxide. 9. The laminated structure has a halogen atom-containing resin layer (A)
and adhesive layer (B), olefin polymer, polyamide resin, ethylene-vinyl acetate copolymer or saponified product thereof, polyester resin, polystyrene resin, ABS resin, polycarbonate resin, polyvinyl alcohol. from polyphenylene oxide resin, polyphenylene sulfide resin, polyether/ether ketone resin, polyether sulfone resin, polyamideimide resin, polyimide resin, polyacetal resin, polysulfone resin, polyarylate resin, polyetherimide resin, polyparabanic acid resin. The laminated structure according to any one of claims 1 to 8, which has a multilayer structure with at least one synthetic resin layer selected from the group consisting of: 10. The laminated structure has a halogen atom-containing resin layer (A
) and an adhesive layer (B) with at least one member selected from the group consisting of rubber, metal, FRP board, wood, glass, ceramic, concrete, plaster, nonwoven fabric, woven fabric, and paper. The laminated structure according to any one of claims 1 to 8, consisting of: