JPH0458383B2 - - Google Patents

Description

[Detailed description of the invention]

(a) Industrial application field The present invention relates to a laminate, and more specifically, a laminate consisting of at least two layers, an ultra-high molecular weight polyethylene layer and an adhesive layer, which can be easily adhered to other base materials through secondary processing. The present invention relates to a laminate that can be used. (b) Conventional technology Ultra-high molecular weight polyethylene has better impact resistance, abrasion resistance, and
Although it has excellent sliding properties, sound deadening properties, stress and crack resistance, and low temperature resistance, secondary processing such as molding and fusing is difficult, so it has not yet been widely used. Ultra-high molecular weight polyethylene has poor fluidity even when heated above its melting point, making it difficult to mold.For example,
For the production of ultra-high molecular weight polyethylene sheets, conventional extrusion molding cannot be applied, so the sheet is first formed into a rod or plate shape using a mold press, and then the molded product is cut (SKIVE) into a sheet. Furthermore,
It is extremely difficult to use this sheet and apply it by fusing or adhering it to other base materials through secondary processing because there is no adhesive with sufficient adhesive strength. Conventionally, ultra-high molecular weight polyethylene (hereinafter referred to as
One of the applications in which UHMW-PE (abbreviated as UHMW-PE) is in high demand is as a lining material for hoppers, shooters, conveyors, etc. Currently, these inner lining methods are attached with screws or the like because there is no excellent adhesive as mentioned above. On the other hand, as a laminate of UHMW-PE and other base materials or a manufacturing method thereof, Japanese Patent Publication No. 59-5429, Japanese Patent Application Laid-Open No. 58-20273, Japanese Patent Application Laid-open No. 31145-1987, etc. have been proposed. However, in both cases, the adhesive strength of the laminate is weak and the secondary processability is also difficult, making them unsuitable for practical use. (c) Problems to be solved by the invention In view of the above points, the inventors have
heat resistance, rigidity, etc. without sacrificing the excellent physical properties of
The object of the present invention is to provide a laminate that compensates for the drawbacks of UHMW-PE, can be easily subjected to secondary processing such as heat fusion and adhesion with other base materials, and has strong adhesive strength. (d) Means for solving the problems The present invention provides a laminate comprising at least two layers: an ultra-high molecular weight polyethylene layer having a viscosity average molecular weight of 1 million or more and an adhesive layer, wherein the adhesive layer has: a) a density of 0.86 to 0.86; 0.94 g/cm ³ , b) Boiling n-hexane insoluble matter is 10% by weight or more, c) Maximum peak temperature (Tm) shown by differential scanning calorimetry (DSC) is 100°C or more, Ethylene-α-olefin An adhesive resin obtained by modifying a copolymer or an olefinic polymer composition containing the copolymer as a main component in the presence of an unsaturated carboxylic acid or a derivative thereof and an organic peroxide, or the adhesive resin. The object of the present invention is to provide a laminate of ultra-high molecular weight polyethylene, which is an olefin-based polymer containing: The ethylene-α-olefin copolymer used in the present invention is a copolymer of ethylene and α-olefin having 3 to 12 carbon atoms. Specific α-olefins include propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, decene-1, dodecene-1, and the like. α- in ethylene-α-olefin copolymer
Olefin content is 2-40 mol%, even 5-20
Preferably it is mol%. Below, ethylene used in the present invention and α-
A method for producing an olefin copolymer will be explained. First, the catalyst system used is a combination of a solid catalyst component containing magnesium and titanium with an organoaluminum compound. Examples of the solid catalyst component include magnesium metal, magnesium hydroxide, magnesium carbonate, magnesium oxide,
Oxygen-containing compounds such as magnesium chloride, double salts, double oxides, carbonates, chlorides, or hydroxides containing magnesium atoms and metals selected from silicon, aluminum, and calcium, as well as these inorganic solid compounds Examples include those in which a titanium compound is supported by a known method on an inorganic solid compound containing magnesium, such as one treated or reacted with a sulfur-containing compound, an aromatic hydrocarbon, or a halogen-containing substance. Examples of the above oxygen-containing compounds include organic oxygen-containing compounds such as water, alcohol, phenol, ketone, aldehyde, carboxylic acid, ethyl, polysiloxane, and acid amide, and inorganic oxygen-containing compounds such as metal alkoxides and metal oxychlorides. can be exemplified. Examples of sulfur-containing compounds include thiol,
Examples include organic sulfur-containing compounds such as thioethers, and inorganic sulfur compounds such as sulfur dioxide, sulfur trioxide, and sulfuric acid. As aromatic hydrocarbons,
benzene, toluene, xylene, anthracene,
Examples include various monocyclic and polycyclic aromatic hydrocarbon compounds such as phenanthrene. Examples of the halogen-containing substance include compounds such as chlorine, hydrogen chloride, metal chlorides, and organic halides. Examples of the titanium compound include titanium halides, alkoxy halides, alkoxides, and halogenated oxides. As the titanium compound, a tetravalent titanium compound and a trivalent titanium compound are suitable. Specifically, as a tetravalent titanium compound, the general formula Ti (OR) n x 4-n (where R number of carbon atoms is 1 to 20 alkyl group, aryl group or aralkyl group, X represents a halogen atom, n is 0≦n≦4), and titanium tetrachloride, titanium tetrabromide, titanium tetraiodide , monomethoxychlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, Triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxychlorotitanium,
Examples include monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium, and tetraphenoxytitanium. As trivalent titanium compounds, titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide are combined with hydrogen, aluminum, titanium, or the periodic table ~
Examples include titanium trihalides obtained by reduction with organometallic compounds of group metals. Also general formula
4 represented by Ti(OR)m×4-m (where R represents an alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms, X represents a halogen atom, and m0<m<4) A trivalent titanium compound obtained by reducing a valent halogen alkoxy titanium with an organometallic compound of a group metal of the periodic table. Among these titanium compounds, tetravalent titanium compounds are particularly preferred. Specific examples of these catalysts include, for example:
MgO−RX−TiCl ₄ system (Special Publication No. 51-3514),
Mg- _SiCl4 -ROH- _TiCl4 system
Publication No.), MgCl ₂ −Al(OR) ₃ −TiCl ₄ system (Special Publication No. 1973), MgCl 2 −Al(OR) 3 −TiCl 4
-152 Publication, Special Publication No. 52-15111), MgCl ₂
-SiCl ₄ -ROH-TiCl ₄ system (Japanese Patent Application Publication No. 1984-106581), Mg (OOCR) ₂ -Al (OR) ₃ -TiCl ₄ system (Japanese Patent Publication No. 11710/1981), Mg-POCl ₃ - TiCl ₄ (Japanese Patent Publication No. 51-153), MgCl ₂ -AlOCl-TiCl ₄ system (Japanese Patent Publication No. 54-15316), MgCl ₂ -Al(OR)n
×3-n-Si(OR')m× ₄ -m-solid catalyst component such as TiCl4 system (JP-A-56-95909) (In the above formula, R and R' are organic residues, represents a halogen atom) in combination with an organoaluminum compound is an example of a preferable catalyst system. Examples of other catalyst systems include solid catalyst components such as
Using a reaction product of an organomagnesium compound such as a so-called Grignard compound and a titanium compound,
An example of a catalyst system is a combination of this and an organoaluminum compound. Examples of organomagnesium compounds include general formulas RMgX,
Organomagnesium compounds such as R ₂ Mg, RMg (OR) (where R is an organic residue having 1 to 20 carbon atoms, and X is a halogen) and ether complexes thereof,
Further, these organomagnesium compounds may be modified by adding other organometallic compounds, such as various compounds such as organosodium, organolithium, organopotassium, organoboron, organocalcium, and organozinc. Specific examples of these catalyst systems include, for example:
RMgX-TiCl ₄ series (Special Publication No. 50-39470)
RMgX-Phenol-TiCl ₄ system (Special Publication 1984-
12953), RMgX-halogenated phenol-TiCl ₄ system (Japanese Patent Publication No. 12954-1987), RMgX-
Examples include combinations of organoaluminium compounds with solid catalyst components such as CO ₂ -TiCl ₄ (JP-A-57-73009). In addition, as an example of another catalyst system, a solid material obtained by contacting an inorganic oxide such as SiO ₂ or Al ₂ O ₃ with a solid catalyst component containing at least magnesium and titanium is used as a solid catalyst component. ,
A combination of this and an organoaluminum compound can be exemplified. Examples of inorganic oxides include CaO, B ₂ O ₃ , SnO ₂ and the like in addition to SiO ₂ and Al ₂ O ₃ , and double oxides of these oxides can also be used without any problem. Any known method can be used to bring these various inorganic oxides into contact with the solid catalyst component containing magnesium and titanium. That is, a method of reacting in the presence or absence of an inert solvent at a temperature of 20 to 400°C, preferably 50 to 300°C for usually 5 minutes to 20 hours, a method of co-pulverization, or a combination of these methods as appropriate. The reaction may be carried out by Specific examples of these catalyst systems include, for example, the SiO ₂ -ROH-MgCl ₂ -TiCl ₄ system (Japanese Patent Application Laid-Open No.
47407), _SiO2 -R-O-R'-MgO- _AlCl3
−TiCl ₄ system (JP-A-57-187305), SiO ₂ −
MgCl ₂ −Al(OR) ₃ −TiCl ₄ −Si(OR′) ₄ series (JP-A-Sho
No. 58-21405) (in the above formula, R and R' represent hydrocarbon residues), and other combinations of organoaluminum compounds can be mentioned. In these catalyst systems, a titanium compound can be used as an adduct with an organic carboxylic acid ester, or the above-described magnesium-containing inorganic solid compound can be used after being brought into contact with an organic carboxylic acid ester. . Moreover, there is no problem in using an organoaluminum compound as an adduct with an organic carboxylic acid ester. Furthermore, in all cases it is also possible to use catalyst systems prepared in the presence of organic carboxylic esters without any problems. Here, various aliphatic, alicyclic, and aromatic carboxylic esters are used as the organic carboxylic ester, and aromatic carboxylic esters having 7 to 12 carbon atoms are preferably used. Specific examples include alkyl esters of benzoic acid, anisic acid, toluic acid, such as methyl and ethyl. A specific example of an organoaluminum compound to be combined with the above-mentioned solid catalyst component is the general formula
R ₃ Al, R ₂ AlX, RAlX ₂ , R ₂ AlOR, RAl(OR)
An organoaluminum compound _of X and R ₃ Al ₂
may be the same or different), and triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diethylaluminum ethoxide, ethylaluminum sesquichloride, and mixtures thereof are preferred. Can be mentioned. The amount of the organoaluminum compound to be used is not particularly limited, but it can usually be used in an amount of 0.1 to 1000 times the amount of the titanium compound. Furthermore, by bringing the catalyst system into contact with an α-olefin and then using it in the polymerization reaction, the polymerization activity can be greatly improved and the system can be operated more stably than in the case of no treatment. Various α-olefins can be used as the α-olefin used at this time, but α-olefins having 3 to 12 carbon atoms are preferable, and α-olefins having 3 to 8 carbon atoms are more preferable.
-Olefins are preferred. Examples of these α-olefins include propylene, butene-olefin, etc.
Examples include 1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, dodecene-1, and mixtures thereof. The temperature and time during the contact between the catalyst system and the α-olefin can be selected within a wide range, for example,
The contact treatment can be carried out at ~200°C, preferably 0~110°C, for 1 minute to 24 hours. The amount of α-olefin to be contacted can be selected within a wide range, but usually, 1 to 50,000 g of α-olefin is used per 1 g of the solid catalyst component, preferably 5 to 30,000 g, and 1 to 500 g of α-olefin is used per 1 g of the solid catalyst component. It is desirable to react α-olefin. At this time, the pressure at the time of contact can be arbitrarily selected, but it is usually desirable to contact under a pressure of -1 to 100 kg/cm ² ·G. In the α-olefin treatment, the entire amount of the organoaluminum compound used may be combined with the solid catalyst component and then brought into contact with the α-olefin, or a part of the organoaluminum compound used may be combined with the solid catalyst component. After combining with α−
The polymerization reaction may be carried out by contacting with olefin and adding the remaining organoaluminum compound separately during polymerization. In addition, there is no problem even if hydrogen gas coexists during the contact between the catalyst system and the α-olefin.
There is no problem even if other inert gases such as nitrogen, argon, helium, etc. coexist. The polymerization reaction is carried out in the same manner as a typical olefin polymerization reaction using a Ziegler type catalyst. That is, all reactions are carried out in a gas phase, in the presence of an inert solvent, or using the monomer itself as a solvent in a state in which oxygen, water, etc. are substantially excluded. The polymerization conditions for olefin are temperatures of 20 to 300℃, preferably 40 to 200℃.
℃, and the pressure is normal pressure to 70 kg/cm ² ·G, preferably 2 kg/cm ² ·G to 60 kg/cm ² ·G.
Although the molecular weight can be controlled to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, it is effectively carried out by adding hydrogen to the polymerization system. Of course, a two-stage or more multi-stage polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any problem. In the present invention, if the density of the ethylene-α-olefin copolymer exceeds 0.94 g/cm ³ , the adhesive resin will not have excellent adhesive properties, and the density will be 0.86 g/cm ³ .
If the adhesive resin is less than 100%, the melting point of the adhesive resin becomes low and cannot withstand use at high temperatures, and the strength of the adhesive layer itself decreases, resulting in a low apparent adhesive force. Furthermore, if the boiling n-hexane insoluble content of the ethylene-α-olefin copolymer is less than 10% by weight, the amorphous portion and low molecular weight components will increase, and the adhesive strength required as an adhesive will not be sufficiently exhibited. On the other hand, if the maximum peak temperature (Tm) in differential scanning calorimetry (DSC) is less than 100°C, the heat resistance of the adhesive is poor. The method for measuring the boiling n-hexane insoluble matter and DSC in the present invention is as follows. [Measurement method for boiling n-hexane insoluble matter] A sheet with a thickness of 200 μm was formed using a heat press, and three sheets of 20 mm x 30 mm in length and width were cut out from the sheet, and the sheets were passed through a double-tube Soxhlet extractor. Extraction is carried out using boiling n-hexane for 5 hours. After taking out the n-hexane insoluble matter and vacuum drying (7 hours, under vacuum, 50°C), boiling n-hexane was removed using the following formula.
-Calculate the hexane insoluble content. Boiling n-hexane insoluble content (weight %) = (extracted sheet weight / unextracted sheet weight) x 100 (weight %) [Measurement method by DSC] Weigh approximately 5 mg of sample from a 100 μm thick hot press-molded film. Then, it was set in a DSC device, heated to 170°C, held at that temperature for 15 minutes, and then cooled to 0°C at a cooling rate of 2.5°C/min. Next, from this state, the temperature is raised to 170°C at a heating rate of 10°C/min, and measurement is performed. The temperature at the position of the maximum peak that appears during the temperature increase from 0°C to 170°C is defined as Tm. The ethylene-α-olefin copolymer used in the present invention is clearly distinguished from the ethylene-α-olefin copolymer obtained by using vanadium as a solid catalyst component. That is, conventional ethylene propylene copolymers and the like have almost no crystallinity, and even if crystal parts exist, they are in very small amounts, and the maximum peak temperature (Tm) measured by DSC is less than 100°C. This indicates that it cannot be used as an adhesive resin for applications requiring heat resistance, adhesive strength, etc. Furthermore, unlike titanium, vanadium, which is present in the copolymer as a catalyst residue, poses a toxicity problem, so a catalyst removal process is essential.However, when titanium is used, there is no problem of toxicity due to the catalyst residue. The copolymer of the present invention, which uses a highly active catalyst in combination with a magnesium support, is extremely economical and preferable because a catalyst removal step is not necessary. In addition, in the present invention, the above ethylene-α
- A composition with an olefin polymer containing olefin as a main component can also be used as the base polymer of the adhesive resin, but the composition ratio of the ethylene-α-olefin copolymer and the olefin polymer is - The content of the olefin copolymer is 60% by weight or more, preferably 70% by weight or more. The above olefin polymers include polyethylene, polypropylene, polybutene-1, poly-4
- Ethylene, propylene, butene-1, 4-methyl-pentene-1, hexene-1, excluding olefin homopolymers such as methyl-pentene-1, or ethylene-α-olefin copolymers in the above specified range, Intercopolymers such as octene-1,
Ethylene-propylene copolymer rubber (EPR), ethylene-propylene-diene copolymer rubber (EPDM), copolymers of ethylene and vinyl esters, unsaturated carboxylic acids, unsaturated carboxylic acid esters, polyisobutylene and their Examples include mixtures. Examples of the unsaturated carboxylic acids used in the present invention include monobasic acids and dibasic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, and citraconic acid. Examples of derivatives of unsaturated carboxylic acids include metal salts, amides, imides, esters, and anhydrides of the unsaturated carboxylic acids, and among these, maleic anhydride is most preferred. The amount of the unsaturated carboxylic acid or its derivative (hereinafter simply referred to as unsaturated carboxylic acid) to be added is based on the ethylene-α-olefin copolymer or the olefin polymer composition containing the copolymer as the main component. An amount of unsaturated carboxylic acid of 0.05 to 10% by weight, preferably 0.1 to 7% by weight, is added and heated in the presence of an organic peroxide to form a reaction. The above reaction can be carried out by melt-mixing in an extruder or a kneader such as a Banbury mixer without a solvent, or with aromatic hydrocarbons such as benzene, xylene, and toluene, and aliphatic hydrocarbons such as hexane, heptane, and octane. Although there are no particular limitations, it is preferable to carry out the reaction in an extruder for reasons such as ease of operation, excellent economic efficiency, and continuity with subsequent processes. . When the amount of unsaturated carboxylic acid exceeds 10% by weight, decomposition and crosslinking reactions may occur in addition to addition reactions, and when it is less than 0.05% by weight, the objective of improving the adhesiveness of the present invention may not be achieved. do not have. Examples of organic peroxides include benzoyl peroxide, lauryl peroxide, azobisisobutyronitrile, dicumyl peroxide, t-butyl hydroperoxide, α,α'-
Bis(t-butylperoxydiisopropyl)benzene, di-t-butylperoxide, 2,5
-di(t-butylperoxy)hexyne etc. are preferably used, and the total amount of the reaction product of the rubber and unsaturated carboxylic acid and the olefinic polymer is 100%.
0.005 to 2.0 parts by weight, preferably 0.01 parts by weight
Used in the range of ~1.0 parts by weight. If the amount of organic peroxide added is less than 0.005 parts by weight, the modification effect will not be exhibited substantially, and even if it is added in excess of 2.0 parts by weight, it will be difficult to obtain any further effect, and it may be excessive. This may cause decomposition or crosslinking reactions. The laminate of the present invention is basically a laminate including at least two layers, an ultra-high molecular weight polyethylene layer and an adhesive layer, but may also include other bases bonded via the ultra-high molecular weight polyethylene layer and the adhesive layer. Materials include polyamide resin, polyvinylidene chloride resin,
Saponified ethylene-vinyl acetate copolymer, polyester resin, polyvinyl chloride resin, polystyrene resin, ABS resin, polycarbonate resin, polyvinyl alcohol resin, fluorine resin, polyphenylene oxide resin, polyphenylene resin Synthetic resins such as rensulfide resin, polyether/etherketone resin, polyamideimide resin, polyimide resin, polyacetal resin, polysulfone resin, polyarylate resin, polyetherimide resin, polybalabanic acid resin, ethylene-propylene copolymer rubber , ethylene-propylene-
Rubbers such as synthetic rubber and natural rubber such as diene copolymer rubber, polybutadiene rubber, butadiene-styrene copolymer rubber, butadiene-acrylonitrile rubber, polychloroprene rubber, acrylic rubber, silicone rubber, aluminum, iron, zinc, copper Metals such as plywood, wood such as plywood, glass, ceramics, concrete, plaster, etc.
Examples include woven fabrics, nonwoven fabrics, and papers made of asbestos, FRP, natural fibers, synthetic fibers, or mineral fibers such as carbon fibers, aramid fibers, and metal fibers. The laminate of the present invention has an ultra-high molecular weight polyethylene layer.
It is basically a laminate containing at least two layers: (A) and an adhesive layer (B), A/B, B/A/B, A/
B/C (here, C is another dissimilar material layer), A/B/C/B, B/A/B/A, C/
It includes multilayer laminates such as 3 layers, 4 layers, or 5 layers such as B/A/B, C/B/A/B/C, etc. Methods for producing the laminate of the present invention include compression molding, transfer molding, injection molding, extrusion molding,
Methods such as air pressure (vacuum) molding, press molding, and rolling are not particularly limited. For example, preformed
It can be manufactured by laminating a UHMW-PE sheet, an adhesive sheet, and, if necessary, sheets of different materials, heating to a predetermined temperature, and rolling. There is also a method (Japanese Patent Application No. 59-11393) of continuously manufacturing a laminated sheet from UHMW-PE powder or a preformed sheet (Japanese Patent Application No. 154523/1982). The form of the laminate of the present invention is not particularly limited, such as film, sheet, tube, plate, tube, bottle, container, injection molded product, etc. (E) Functions and Effects of the Invention The laminate of the present invention is a laminate consisting of at least two layers: an ultra-high molecular weight polyethylene layer, another base material, and an adhesive layer having strong adhesive strength, and can be easily fused and bonded. , secondary processing such as adhesion is possible. For example, by taking advantage of the excellent physical properties of ultra-high molecular weight polyethylene, such as abrasion resistance, impact resistance, sliding properties, sound deadening properties, stress crack resistance, and low temperature resistance, it can be used in hoppers, shooters, conveyors, etc. It can be easily adhesively processed and used as upholstery, skis, sliding sheets for skis, sliding sheets for snowboards, etc. In addition, multilayer laminates can also be used as gasoline tanks, heat storage tanks for solar houses, water tanks, low-temperature storage containers, etc. by taking advantage of their respective properties. Furthermore, by using a sheet containing a conductive filler such as carbon fiber or carbon black, it can be applied to electronic materials such as containers for electronic devices or dust removal mats laminated with rubber. (F) Examples The present invention will be explained in more detail below using Examples and Comparative Examples. Examples 1-3 Polymerization of ethylene and propylene was carried out using a solid catalyst component obtained from substantially anhydrous magnesium chloride, 1,2-dichloroethane and titanium tetrachloride, and a catalyst consisting of triethylaluminum. Three types of ethylene-propylene copolymers were obtained. (A) Density 0.870g/cm ³ , maximum peak of DSC (Tm)
Ethylene-propylene copolymer with 45% n-hexane insoluble content at 119.0°C. (B) Density 0.887g/cm ³ , maximum peak of DSC (Tm)
Ethylene-propylene copolymer with 50% n-hexane insoluble content at 119.5°C. (C) Density 0.908g/cm ³ , maximum peak of DSC (Tm)
Ethylene-propylene copolymer with 50% n-hexane insoluble content at 121.5°C. 0.25 parts by weight of maleic anhydride and 0.02 parts by weight of an organic peroxide (2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3) were added to 100 parts by weight of the above three types of copolymers. The mixture was kneaded in a Banbury mixer at 200°C for 15 minutes to obtain a modified adhesive resin. Thickness of the three types of adhesive resins prepared above
An adhesive layer of 500μ thick, this and a 700μ thick ultra-high molecular weight polyethylene (UHMW-PE, viscosity average molecular weight 3.2 million, trade name: Nisseki Taffetalex, manufactured by Nippon Petrochemicals Co., Ltd.) layer and a base material. Saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVAL, trade name: EVAL ED-F, manufactured by Kuraray Co., Ltd.),
Aluminum plate (Al), nylon-6 (hereinafter referred to as PA
Product name: Toray Milan 1046, manufactured by Toray Industries, Inc.), polyethylene terephthalate (hereinafter referred to as PET)
Product name: Kodar PETG6763, manufactured by Eastman Chemical Products Inc.), polyvinylidene chloride (hereinafter abbreviated as PVDC, manufactured by Kureha Chemical Co., Ltd.), and polyvinyl chloride resin (hereinafter abbreviated as PVC). Name: Aron Compound BL, 2M−11
-P, manufactured by Toagosei Co., Ltd.), preheated to 220°C, stacked, and placed in an oven at 220°C for 5 minutes.
After pressurizing at 100Kg/cm ² and slowly cooling, test piece (25mm width)
was created and the tensile speed was 50 mm/min using a tensile tester.
Table 1 shows the adhesive strength measured by peeling at 180°. Example 4 Linear low density polyethylene (hereinafter abbreviated as LLDPE, density 0.922 g/cm ³ , maximum peak (Tm) of DSC) 122 was added to 70 parts by weight of the adhesive resin (B) used in Example 2.
°C, n-hexane insoluble content 97.2%, melt index 2g/10 minutes, product name: Nisseki Linirex
30 parts by weight of AF3340 (manufactured by Nippon Petrochemicals Co., Ltd.) was added to a Banbury mixer and mixed to prepare an adhesive resin composition. Using this as an adhesive layer, a laminate was obtained in the same manner as in Example 1. , the adhesive strength was evaluated. The results are shown in Table 1. Example 5 A laminate was prepared in the same manner as in Example 1 except that LLDPE used in Example 4 was used, and the adhesive strength was evaluated. The results are shown in Table 1. Comparative Example 1 High-density polyethylene (hereinafter abbreviated as HDPE, density 0.948 g/cm ³ , melt index 0.03 g/10
(trade name: Nisseki Stafrene E903, manufactured by Nippon Petrochemicals Co., Ltd.) was modified in the same manner as in Example 1, a laminate was prepared, and the adhesive strength was evaluated. The results are shown in Table 1. Comparative Example 2 Ethylene-vinyl acetate copolymer (hereinafter referred to as EVA)
abbreviated as, density 0.928g/cm ³ , melt index
1.0g/10 minutes, Product name: Nisseki Rexron V251,
Example 1 using adhesive layer (manufactured by Japan Petrochemical Co., Ltd.)
A laminate was prepared in the same manner as above, and the adhesive strength was evaluated. The results are shown in Table 1. Example 6 Ethylene-butene-1 copolymer (hereinafter referred to as
Abbreviated as MDPE, density 0.940g/cm ³ , DSC maximum peak (Tm) 127°C, n-hexane insoluble content 99.1%,
Melt index 7.0g/10 minutes, product name: Nisseki Linirex AR4820, manufactured by Nippon Petrochemical Co., Ltd.)
was modified in the same manner as in Example 1, a laminate was prepared, and the adhesive strength was evaluated. The results are shown in Table 1.

[Table] Examples 7 to 13 The modified LLDPE of Example 5 was used as the adhesive layer, and polycarbonate resin (hereinafter abbreviated as PC, trade name: Iupilon) was used as the base material.
NF2000, manufactured by Mitsubishi Gas Chemical Co., Ltd.), polyphenylene oxide resin (hereinafter abbreviated as PPO, product name: Noryl 731J, manufactured by Engineering Plastics Co., Ltd.), polyphenylene sulfide resin (hereinafter referred to as PPS) Product name: Ryton R-4
manufactured by Philips Chemical Co., Ltd.), glass fiber-filled polyethylene terephthalate (hereinafter abbreviated as FR-PET),
Product name: FR-PET C-3030, Teijin Ltd. product),
FRP board (product name: Rigoratsuku 259, Showa Kobunshi Co., Ltd.)
), kraft paper (basis weight 78g/m ² , Daiko Paper Co., Ltd.)
), polystyrene resin (hereinafter abbreviated as PST),
Product name: UHMW-
It was laminated with PE and the adhesive strength between each layer was measured. The results are shown in Table 2.

【table】

【table】

【table】

Claims (1)

[Claims] 1. A laminate having a laminate as a base comprising at least two layers: an ultra-high molecular weight polyethylene layer having a viscosity average molecular weight of 1 million or more and an adhesive layer, wherein the adhesive layer has: a) a density of 0.86 to 0.86; 0.94 g/cm ³ , b) Boiling n-hexane insoluble matter is 10% by weight or more, c) Maximum peak temperature (Tm) shown by differential scanning calorimetry (DSC) is 100°C or more, Ethylene-α-olefin An adhesive resin obtained by modifying a copolymer or an olefinic polymer composition containing the copolymer as a main component in the presence of an unsaturated carboxylic acid or a derivative thereof and an organic peroxide, or the adhesive resin. An ultra-high molecular weight polyethylene laminate characterized by being an olefinic polymer containing. 2. The ultra-high molecular weight polyethylene laminate according to claim 1, wherein the amount of the unsaturated carboxylic acid or its derivative added is in the range of 0.05 to 10% by weight. 3. The ultra-high molecular weight polyethylene laminate according to claim 1 or 2, wherein the unsaturated carboxylic acid or its derivative is maleic anhydride. 4. The laminate is made of polyamide resin, polyvinylidene chloride resin, saponified ethylene-vinyl acetate copolymer, polyester resin, polyvinyl chloride resin, Polystyrene resin, ABS resin,
Polycarbonate resin, polyvinyl alcohol resin, fluorine resin, 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,
The ultra-high molecular weight polyethylene laminate according to any one of claims 1 to 3, which has a multilayer structure with at least one synthetic resin layer selected from the group consisting of polyvalabanic acid resins. 5 The laminate may be made of rubber, metal, FRP board, wood, etc. via the ultra-high molecular weight polyethylene layer and adhesive layer.
A laminate of ultra-high molecular weight polyethylene according to any one of claims 1 to 3, comprising a multilayer structure selected from the group consisting of glass, ceramic, concrete, plaster, nonwoven fabric, woven fabric, and paper.