JPH03169547A - Laminate - Google Patents

Abstract

PURPOSE:To obtain a laminate having excellent low-temperature heat sealing properties, abounding in flexibility and having superior heat resistance by constituting the laminate by using a specific polypropylene resin. CONSTITUTION:One material layer is formed by using soft polypropylene as a main component. The material layer may contain a material layer composed of either one of a thermoplastic resin or a thermosetting resin. Or the material layer may contain a material layer consisting of either one of a metal, a rubber, cloth, paper, wood, cellophane or leather. A polypropylene group polymer and a random copolymer are adjusted by either of a vapor-phase one-stage polymerization method or a slurry one-stage polymerization method.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a laminate suitable for use as exterior and interior materials for various products, agricultural films, steel coating materials, and the like.

[Prior art] Various homotype and Solock type polypropylene resins (PP) have been known, and these P
Sheets and packaging materials made by combining P and other materials are used in various fields. [Problems to be solved by the invention] However, conventional polypropylene resins generally have a high welding temperature of 160"C or higher, and have a flexural modulus of 9.
It had hard properties at 0 0 0 kg/c1 or more. Therefore, sheet materials, packaging materials, etc. formed from conventional laminates containing polypropylene resin have poor heat-sealability and lack flexibility, making them not necessarily easy to handle depending on the intended use. . Also,
Conventionally, straight-button low-density polyethylene (LLDPE) has been used as a sealant between each material, and its heat resistance is as low as 115-125°C, which may limit its use with fish. Therefore, the present invention aims to provide a laminate that has good low-temperature heat sealability, is highly flexible, and has excellent heat resistance. As a result of intensive research to achieve
The inventors have found that by lowering the welding temperature, the above problems can be solved by providing appropriate flexibility and excellent thermal properties, and based on this knowledge, the present invention has been completed.

That is, the laminate of the present invention is characterized in that at least one material layer is formed mainly from soft polypropylene. Further, as a mode of implementation of the present invention, it may include a material layer made of at least one of thermoplastic resin or thermosetting resin. Alternatively, it may include a material layer made of at least one of metal, rubber, cloth, paper, wood, cellophane, or leather. In this specification, "soft polypropylene" refers to homopolymers or copolymers described in (1) to (4) below,
Furthermore, it means any of the MX precepts containing these polymers. (1) (i) 10 to 90% by weight of boiling butane-soluble polypropylene with a solid viscosity of 1.2 dm/g or more
and (ii) an intrinsic viscosity of 0.5 to 9. Polypropylene polymer (a), (2) (
i) α-olefin unit content is 0.1 to 5 mol%, (ii) boiling hexane soluble content having an intrinsic viscosity of 1.2 dl/g or more is 20 to 99.9% by weight,
and (ii+) the tensile modulus is 5 0 0 0 Kg/
Random copolymer of propylene and α-olefin having 4 to 30 carbon atoms (b), (3) (i) @ polypropylene polymer (a) 1O~
95% by weight. (ii) Ethylene unit content is 10~
Ethylene-propylene copolymer (c) having an ethylene unit content of 60 mol% and a solid viscosity of 0.5 to 7.0 dl7g and/or (ii) an ethylene unit content of 10 to 60 mol% and a polyene unit content of 1 to 10 mol%, and the intrinsic viscosity is 0.
5-7. A brobylene system consisting of 90 to 5% by weight of ethylene-propylene-borien copolymer (c') with Odi/g! (d), and (4) (i) 10 to 95% by weight of the random copolymer (b). (ii) The ethylene-propylene copolymer (C) and/or the ethylene-propylene-boriene copolymer (c') 90-5
A propylene-based composite (e) consisting of a melon amount%.

In addition, it is particularly preferable that the polypropylene polymer (a) has the following properties (i) to (iv). (i) ``G:-In the bentad fraction by NMR, rrrr/1-msam is 20% or more. (
ii) The melting peak temperature (Tm) determined by ΔI4 using a differential octometer (DSC) is 150'C or higher. (iii
) Enthalpy of fusion (△H) measured by DSC or 1
It is less than 0 0 J/g.

(iv) Domain structure is observed in transmission electron microscopy. Among the flexible polypropylenes used in the present invention, the above-mentioned polypropylene polymer (a) and random copolymer (b)
can be produced by yJ, for example, by either the gas phase one-stage polymerization method or the slurry one-stage polymerization method described below. The preparation methods for these will be explained in order below. The catalyst system used in the gas phase one-stage polymerization method is, for example, (■)
(i) crystalline polyolefin and (ii) magnesium;
A solid component consisting of titanium, a halogen atom, and a solid catalyst component consisting of an electron-donating compound, (■) an organoaluminum compound (m) an alkoxy group-containing aromatic compound, and (IV)
It consists of a combination of electron-donating compounds. The solid component (I) is crystalline polyolefin (i)
0.00 solid catalyst fraction (ii) for lffii part
5 to 30 parts by weight (preferably 0.02 to lO'rfLf
fi part).

The solid fraction (I) may be, for example, a solid catalyst fraction (ii).
), an organoaluminum compound, and optionally an electron-donating compound, it can be prepared by a method of prepolymerizing an olefin (pre-a polymerization method). Here, the solid catalyst component (ii) essentially contains magnesium, titanium, a halogen atom, and an electron donating compound, and this is achieved by bringing the magnesium compound, titanium compound, and electron donating compound into contact with each other. It can be prepared. Examples of the magnesium compound include magnesium cyhalide such as magnesium cyclolide, magnesium oxide, magnesium hydroxide, hydrotalcite, magnesium carboxylate, alkoxymagnesium such as diethoxymagnesium, allyloxymagnesium, alkoxymagnesium halide,
Examples include alkylmagnesiums such as allyloxymagnesium halide and ethyltutylmacnesium, alkylmagnesium halides, and reaction products of organomagnesium compounds with electron donors, halosilanes, alkoxysilanes, silanols, and aluminum compounds. Among these, magnesium halide, alkoxymagnesium, alkylmagnesium, and alkylmagnesium halide are preferred. Moreover, these magnesium compounds may be used in one type or in combination of two or more types. Examples of titanium compounds include tetramethoxytitanium, tetraethoxytitanium, tetra-n-broboxytitanium, tetraisoproboxytitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium, tetracyclohexyloxytitanium, tetraphenoxytitanium, etc. Tetrahalogenated titanium such as tetraalkoxytitanium, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, methoxytitanium trichloride, ethoxytitanium trichloride, proboxytitanium trichloride, n-butoxytitanium trichloride, ethoxytitanium Trihalogenated alkoxytitanium such as tribromide, dihalogenated dialkoxytitanium such as dimethoxytitanium dichloride, diethoxytitanium dichloride, diproboxytitanium dichloride, di-n-proboxytitanium dichloride, diethoxytitanium dibromide, trimethoxy Examples include monohalogenated trialkoxytitanium such as titanium chloride, triethoxytitanium chloride, tribroboxytitanium chloride, and tri-n-butoxytitanium chloride, but among these, high halogen-containing titanium compounds, especially titanium tetrachloride, etc. It is suitable. These titanium compounds may be used alone or in combination of two or more. The electron-donating compound is an organic compound containing oxygen, nitrogen, phosphorus, sulfur, silicon, etc., and is used as a base material to improve regularity in the polymerization of propylene.

Examples of such electron-donating compounds include esters, thioesters, amines, ketones, nitriles, phosphines, ethers, thioethers, acid anhydrides, acid halide granules, acid amides, and aldehydes. Examples include organic acids, etc. Furthermore, for example, cyphenyldimethoxysilane, diphenyldiethoxysilane,
Organosilicon compounds such as cybenzyldimethoxylane, tetramethoxysilane, tetraethoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, phenyltrimethoxysilane, penzyltrimethoxysilane, phthalic acid Aromatic dicarboxylic acid esters such as 1-n-butyl and diisobutyl phthalate, alkyls of carbons a1 to 4 of aromatic monocarboxylic acids such as ben, q-aroic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, toluic acid, etc. ester, isobrobyl methyl ether, inbropylethyl ether, t-butyl methyl ether, t-butyl ethyl ether, t-butyl-n-propylether, t-
Asymmetric ethers such as butyl n-butyl ether, t-amylmethyl ether, t-amyl ethyl ether,
2,2゜-azobis(2-ethylpropane), 2,2-
Azobis(2-ethylbroban), 2.2′-azobis(2-methylbentane), a,a°-azobisisobutyronitrile, 1.1′-azobis(1-cyclohexanecarboxylic acid), (l- phenylmethyl) monoazodiphenylmethane, 2-phenylazo-2,4-dimethyl-4-
Examples include azo compounds in which a sterically hindering substituent is bonded to an azo bond, such as tricybentanenitrile, and these compounds may be used singly or in combination of two or more. Specifically, dimethyl phthalate, diethyl phthalate, dibropylphthalate, diisobutyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl isobutyl phthalate, ethyl propyl phthalate, ethyl isobutyl phthalate, probylisottylphthalate, dimethyl terephthalate, Diethyl terephthalate, sibropyl terephthalate, diisobutyl terephthalate, methyl ethyl terephthalate, methylpropyl terephthalate, methyl isobutyl terephthalate, ethylpropyl terephthalate, ethyl isobutyl terephthalate, probyl isobutyl terephthalate, dimethyl isophthalate, diethyl isophthalate, dibropyl isophthalate, cyisobutyl isophthalate,
Aromatic dicarboxylic acid diesters such as methyl ethyl isophthalate, methyl propyl isophthalate, methyl isobutyl inphthalate, ethyl propyl isophthalate, ethyl isobutyl isophthalate and probyl isobutyl isophthalate, methyl formate, ethyl acetate, vinyl acetate, probyl acetate , octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl acetate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, ethyl benzoate , brovyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethyl toluate, amyl toluate, ethyl anisate, ethyl ethoxybenzoate, ethyl P-butoxybenzoate, O - Monoesters such as ethyl chlorobenzoate and ethyl naphthoate, esters having 2 to 18 carbon atoms such as γ-valerolactone, coumarin, phthalide, and ethylene carbonate, organic acids such as benzoic acid and p-oxybenzoic acid, Acid anhydrides such as succinic anhydride, benzoic anhydride, and p-toluic anhydride; 3-carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, penzophenone, and benzoquinone;
~15 ketones, aldehydes with 2 to 15 carbon atoms such as acetaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthylaldehyde, acetyl chloride, penzyl chloride, toluic acid chloride,
Acid halides with a carbon number of 2 to 15 such as anisyl chloride; Ethers, acid amides such as acetic acid amide, benzoic acid ado, toluic acid ado, tributylamine, N,N'-
dimethylpiverazine, tosobenzylamine, aniline,
Examples include amines such as pyridine, picoline, and tetramethylethylenediamine, and nitriles such as acetonitrile, penzonitrile, and tolnitrile. Among these, esters, ethers, ketones and acid anhydrides are preferred, particularly di-n-butyl phthalate,
Suitable examples include aromatic dicarboxylic acid diesters such as diisobutyl phthalate, and alkyl esters having 1 to 4 carbon atoms of aromatic monocarboxylic acids such as benzoic acid, p-methoxybenzoic acid, P-ethoxybenzoic acid, and toluic acid. Aromatic dicarboxylic acid diesters are particularly preferred because they improve catalyst activity and activity persistence.

The solid catalyst fraction (11) is prepared by a known method (JP-A-53-4:1094, JP-A-55-1351).
02, JP-A-55-135103, and JP-A-56-18606). For example, (1) a method of pulverizing a magnesium compound or a complex compound of a magnesium compound and an electron donor in the presence of an electron donor and a grinding aid used as desired, and reacting it with a titanium compound; ) A method in which a liquid magnesium compound having no reducing ability and a liquid titanium compound are reacted in the presence of an electron donor to precipitate a solid titanium complex, (3) the above (1) or (2). ) A method of reacting a titanium compound with the material obtained in (4)
A method of further reacting an electron donor and a titanium compound with the material obtained in (1) or (2) above, (5) a method of reacting a magnesium compound or a complex compound of a magnesium compound and an electron donor with an electron donor, titanium (6) A method in which the compound obtained in (1) to (4) above is treated with a halogen or halogen compound after being crushed in the presence of a compound and a crushing aid used as desired. It can be prepared by a compound treatment method, etc.

Furthermore, methods other than these methods (Japanese Unexamined Patent Publication No. 55-156
205, JP 57-53309, JP 57-19QQQA, JP 57-3 (lQ4G
7, Japanese Unexamined Patent Publication No. 58-47003), the above-mentioned solid catalytic converter (ii) can also be prepared.
In addition, oxides of elements belonging to groups ■ to ■ of the periodic table, for example,
A composite oxide containing at least one oxide of an oxide such as silicon oxide, magnesium oxide, or aluminum oxide or an oxide of an element belonging to Groups ■ to ■ of the periodic table, such as a solid material in which the magnesium compound is supported on silica alumina, etc. , an electron donor, and a titanium compound in a solvent at O~200
2°C, preferably at a temperature in the range of 10-150°C.
By contacting the solid catalyst for ~24 minutes (ii
) can be prepared.

In preparing the solid catalyst fraction (ii), an organic solvent inert to the magnesium compound, electron donor and titanium compound, such as an aliphatic hydrocarbon such as hexane or heptane, benzene or toluene, may be used as a solvent. Aromatic hydrocarbons or halogenated hydrocarbons such as mono- and polyhalogen compounds of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms can be used. Ml of the solid catalyst fraction (ii) thus prepared
The precepts usually have a magnesium/titanium atomic ratio of 2 to 100,
The halogen/titanium atomic ratio is in the range of 5 to 200, and the electron donor/titanium molar ratio is in the range of 0.1 to 10. The above-mentioned solid component (I) can be prepared by prepolymerizing the solid component (ii) thus obtained, an olefin in the presence of an organoaluminum compound, and optionally an electron-donating compound. can. The organoaluminum compound used here has the general formula A R 3pX i-p (1) (R in the formula is an alkyl group having 1 to IO carbon atoms, X is a halogen atom such as chlorine or bromine, and p is 1 Examples of such aluminum compounds include trimethylaluminum, triethylaluminum, triisopropylaluminium, triisophthylaluminium, and trioctylaluminum. Trialkylaluminum such as, diethylaluminum monochloride, diisobrobylaluminium monochloride, diisobutylaluminum monochloride, dialkylaluminum monohalide such as dioctylaluminum monochloride 1~, alkylaluminum sesquihalite such as ethylaluminum sesquichloride, etc. One type of these aluminum compounds may be used, or two or more types may be used in combination.

Further, as the electron-donating compound that may be present depending on the case, the compounds described in relation to the solid catalyst precept (ii) can be used.

In the method for preparing solid bokubun (I), an α-olefin having 2 to 10 carbon atoms such as ethylene, propylene, phthene-1,4-methylbentene-1 is used as the olefin, and the temperature is usually 30 to 80°C, preferably is 55-70'
The prepolymerization is carried out at a temperature in the range of 100° C. to form a crystalline boso-olefin, preferably with a melting point of 100° C. or higher. At this time, the aluminum/titanium atomic ratio of the catalyst system is usually selected in the range of 0.1 to 100, preferably 0.5 to 5, and the electron donating compound/titanium molar ratio is selected in the range of 0 to 50.
．． It is preferably selected within the range of 0.1 to 2. The solid catalyst (I) is prepared by adding the solid catalyst (II), an aluminum compound, and an electron-donating compound (melting point 100"C) to a crystalline powder such as crystalline polypropylene or polyethylene with a uniform particle size. It can also be prepared by a method of dispersing (dispersion method).

Furthermore, the solid fraction (I) can also be prepared by combining the prepolymerization method and the dispersion method described above.

As mentioned above, the catalyst system used in the gas phase one-stage polymerization method consists of a solid fraction (I), an organoaluminum compound (II), an alkoxy group-containing aromatic compound (m), and an electron-donating compound (r).
The organic aluminum compound <II) and the electron-donating compound (IV) can be prepared by contacting them with V), or the compounds explained above can be used, respectively. Further, the alkoxy group-containing aromatic compound (m) can be prepared by, for example, the general formula [wherein Rl is an alkyl group having 1 to 20 carbon atoms, R2 is a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitro group, and m is An integer of 1 to 6, n is an integer of O to (6-m)], and specifically, examples include m-methoxytoluene, 0-methoxyphenol, m-methoxyphenol, 2 -methoxy-4-methylphenol, vinylanineol, p-(1-probenyl)anisole,
p-allylanisole, 1,3-bis(p-methoxyphenyl)-1-bentene, 5-allyl-2-methoxyphenol, 4-allyl-2-methoxyphenol, 4-
Monoalkoxy compounds such as hydroxyloxy 3-methoxybenzyl alcohol, methoxybenzyl alcohol, nitroanisole, nitrophenethole, 0-dimethoxybenzene, m-dimethoxybenzene, p-dimethoxybenzene, 3.4-dimethoxytoluene, 2.6- Dialkoxy compounds such as dimethoxyphenol, l-allyl-3,4-dimethoxybenzene, and 1,3.5-1-rimethoxybenzene, 5-allyl-l,2,3-trimethoxybenzene, 5-allyl-1,2 .4-trimethoxybenzene, 1,2.3-trimethoxy-5-(l-probenyl)benzene, 1,2.4-trimethoxy-5-(
Examples include trialkoxy compounds such as 1-probenyl)benzene, 1,2.3-trimethoxybenzene, and 1,2.4-}-rimethoxybenzene, and among these, dialkoxy compounds and trialkoxy compounds. It is suitable. These alkoxy group-containing aromatic compounds may be used alone or in combination of two or more. In the above-mentioned catalyst system, the solid fraction (I) is used in an amount of 0.0005 to 1 mol per reaction volume in terms of titanium atoms. The amount of the alkoxy group-containing aromatic compound (m) to be used is 0.01 to 500 mol, preferably 1 to 300 mol, per 1 mol of titanium atoms in the solid fraction (I). This usage amount is 0. If the amount is less than 1 mol, the physical properties of the raw aluminum polymer will deteriorate, and if it exceeds 500 mol, the catalytic activity will be decreased, which is undesirable.・40-800). If the atomic ratio is outside this range, sufficient catalytic activity cannot be obtained. Furthermore, an alkoxy group-containing aromatic compound (m) and an electron-donating compound (I
The molar ratio with V) is 1:O. Ol~100 (preferably 1:0.2~100).

In the gas phase one-stage polymerization method, the above-mentioned polypropylene polymer (a) is obtained by homopolymerizing propylene, and propylene and carbon! By copolymerizing with 4 to 30 α-olefins, the above-mentioned random copolymer (b) can be obtained. Molecular weight adjustment can be carried out by known means (eg, adjustment of hydrogen concentration). The polymerization temperature is generally 40-90°C (preferably 60-75°C), and the polymerization pressure is 10°C.
~45 Kg/c1 (preferably 20 ~30
Kg/cm2). The polymerization time is 5 minutes to 10 hours. In the slurry one-stage polymerization method, for example, one of the following two types of catalyst systems can be used. That is, from the combination of (1) (a) a solid fraction whose essential components are magnesium, titanium, a halogen atom, and an electron donor, (b) an aromatic compound containing an alkoxy group, and (c) an organoaluminum compound. A certain catalyst system, or (2) (A) reacting the above (a) solid with (b) an alkoxy group-containing aromatic compound in the presence or absence of (c) an organic alkunium compound. This is a catalyst system that is effective from the combination of a solid catalytic fraction obtained by the above-mentioned method, and (.B) an organoaluminum compound. First, to explain the catalyst system in (1) above, the solid fraction (a) has magnesium, titanium, a halogen atom, and an electron donor as essential components, and a magnesium compound, a titanium compound, and an electron donor. It can be prepared by bringing them into contact with each other. In addition, when preparing this solid component (a), use a solvent that is inert to the magnesium compound, electron donor, and titanium compound, such as an aliphatic hydrocarbon (hexane, hebutane, etc.), an aromatic hydrocarbon, etc. (benzene,
toluene, etc.), or halogenated hydrocarbons (mono- and polyhalogen compounds of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms, etc.) alone or in combination of two or more. You can use it. The magnesium compound, titanium compound, and electron-donating compound used in preparing the solid fraction (a) of the catalyst system (1) are each of the above-mentioned catalyst systems for the gas phase one-stage polymerization method. It can be the same as a compound. Solid fraction (a) can be prepared from these compounds by known methods (for example, the method described in the gas phase one-stage polymerization method).
As the alkoxy group-containing aromatic compound (b) and organoaluminum compound (c) to be brought into contact with the solid part (a) thus obtained, each compound mentioned in relation to the catalyst system of the gas phase one-stage polymerization method may be used. can be used. Regarding the usage amount of each component constituting the catalyst system (1), the solid component (a) is usually equivalent to the reaction volume Ml in terms of titanium atoms.
The alkoxy group-containing aromatic compound (b) is used in an amount of 0.0005 to 1 mol per sentence, and the molar ratio of the alkoxy group-containing aromatic compound (b) to the titanium atoms in the solid component (a) is usually 0.01 to 500 (preferably 1 to 300). It is used at a rate of . If this molar ratio is less than 0.01, the physical properties of the resulting polymer will deteriorate, and if it exceeds 500, the catalytic activity will decrease, which is not preferable. The organoaluminum compound (c) is used in an amount such that the aluminum/titanium atomic ratio is usually 1 to 3,000 (preferably 40 to 800). If this amount exceeds the above range, the catalyst activity will be insufficient. Next, to explain the catalyst system (2), the solid catalyst fraction (A) in this catalyst system (2) is composed of the solid catalyst fraction (A) of the catalyst system (1) and the alkoxy group-containing aromatic compound. It can be prepared by reacting (b) with the organoaluminum compound (c) in the presence or absence of the organoaluminum compound (c). For this preparation, a hydrocarbon solvent (for example, the hydrocarbon solvent used in the preparation of the catalyst system (1)) is generally used.

The reaction temperature is usually 0 to 150°C (preferably 10 to 50°C).
0"C), and if this temperature is below 0℃, the reaction will not proceed sufficiently, and if it exceeds 150"C, side reactions will occur.
Activity decreases. The reaction time varies depending on the reaction temperature, but is usually 1 minute to 20 hours, preferably 10 to 60 minutes.

When preparing the solid catalyst fraction (A) in the presence of the organoaluminum compound (c), the concentration of the aluminum compound (c) is usually 0.05 to 100 mmol/or (preferably 1 to 10 mmol/ sentence). This concentration is 0.
If it is less than 0.5 mmol/cross, the effect of conducting the reaction in the presence of the organoaluminum compound (c) cannot be sufficiently obtained, and if it exceeds 100 mmol/cross, the reduction of titanium in the solid fraction (b) will proceed. As a result, the catalytic activity decreases. On the other hand, in the absence of the organoaluminum compound (c), a solid fraction (a) and an alkoxy group-containing aromatic compound! When preparing a solid catalyst (A) by reacting with IN (b), the alkoxy group-containing compound (b) is a solid catalyst, (a)
The molar ratio to the titanium atoms in the
(preferably 1 to 50), and the concentration of compound (2) is usually 0.01 to 1.
0 mmol/statement (preferably 0.1-2 mmol/statement)
selected within the range. If the ratio of titanium to titanium atoms is outside the above range, it will be difficult to obtain a catalyst with the desired activity. Also, if the concentration is less than 0 or 0 mmol/liter, the volumetric efficiency is low and not practical, and if it exceeds 10 mmol/liter, overreaction tends to occur and the catalytic activity decreases. As the organoaluminum compound (B) in the catalyst system (2), the organoaluminum compounds exemplified in connection with the catalyst for the one-stage gas phase method can be used. Regarding the amount of each component used in the catalyst system (2). The solid catalyst fraction (A) has a reaction volume of 1 in terms of titanium atoms.
per sentence, usually o. The organic aluminum compound (
B) has an aluminum/titanium atomic ratio of usually 1 to 30.
00 (preferably 40 to 800). If this atomic ratio exceeds the above range, the catalytic activity will be insufficient. In the slurry one-stage polymerization method of the present invention, when propylene is homopolymerized, the polypropylene polymer (a
) can be obtained, and propylene and α having 4 to 30 carbon atoms can be obtained.
When copolymerized with an olefin, the above-mentioned random copolymer (b) can be obtained. In the case of slurry one-stage polymerization, the polymerization temperature is usually O~200℃
(preferably 60 to 100°C), and the propylene pressure is usually selected in the range of 1 to 50 Kg/c+a''. Polymerization time of about 5 minutes to 10 hours is sufficient, and the molecular weight of the polymer can be adjusted by known means, for example, by adjusting the hydrogen concentration in the polymerization vessel.Next, among the flexible polypropylenes used in the present invention, propylene-based composite (d) (
a) and ethylene-brobylene copolymer (c) or ethylene-brobylene-boriene copolymer (C")} and propylene-based composition (e) {the random copolymer ( b) and the ethylene-propylene copolymer (c) or the ethylene-propylene-boriene copolymer (C')} can be produced, for example, by the following gas phase multi-stage method, slurry multi-stage method or blending method. The catalyst used in the gas-phase multi-stage polymerization method is the same as the catalyst used in the gas-phase one-stage polymerization method. The polymerization (first stage polymerization) is the same as the gas phase one stage polymerization described above.Therefore, the molecular weight ?A can be determined by known means (for example, adjusting the hydrogen concentration).The polymerization temperature is
Generally, the temperature is 40 to 90°C (preferably 60 to 75°C), the polymerization pressure is 10 to 45 Kg/c+a'' (preferably 20 to 30 Kg/am2), and the polymerization time is 5 minutes to 10 minutes. It is between.

The second to final polymerization (nth stage polymerization) is ethylene-propylene copolymerization or ethylene-propylene-boriene copolymerization. Examples of non-conjugated polyenes that can be used in the copolymer include dicyclobentadiene, tricyclopentadiene, 5-methyl-2,5-norbornasiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-imbropylidene-2-norbornene,
5-Imbrobenyl-2-norbornene. 5-(1-butenine)-2-norbornene, cyclooctashene, vinylcyclohexene, 1,5.9-cyclotodecatosoene, 6-methyl-4.7,8.9-tetrahydroindene, 2-2゛- Dicyclobentenyl, trans-1,2
-divinylcyclobutane, 1,4-hexadiene, 4-
Methyl-1,4-hexacyene, 1,6-octadiene, 1,7-octadiene, 1.8-nonadiene, 1.9
-decacyene, 3,6-dimethyl-1,7-octadiene, 4,5-dimethyl-1,7-octadiene, 1,4
．． Examples include 7-octatriene, 5-methyl-1,8-nonacyene, norbornadiene, and vinylnorbornene. Among these nonconjugated polyenes, cyclobentadiene, 5-ethylidene-2-norbornene, and 1,7-octadiene are particularly preferred. At each polymerization step, molecular weight adjustment is carried out by known means (
For example, this can be done by adjusting the hydrogen concentration.
In the case of ethylene-propylene copolymers, the ethylene unit content can be adjusted by adjusting the feed gas composition. Further, in the case of an ethylene-propylene-boriene copolymer, the amount of polyene unit containing arAm can be determined by changing the amount of the polyene compound charged. The polymerization temperature is 20
~90°C (preferably 40~50°C), and the polymerization pressure is 5~30Kg/c1 (preferably lO~20Kg/c1).
am”) and the polymerization time is 5 minutes to 10 minutes.

Slurry multi-stage polymerization method Also in the slurry multi-stage polymerization method, either catalyst system (1) or (2) used in the slurry one-stage polymerization method can be used. The polymerization order and the number of polymerization stages in the slurry multistage polymerization method are not particularly limited and can be arbitrarily selected. For example, in the first and third stage polymerization, propylene homopolymerization or copolymerization of propylene and an α-olefin having 4 to 30 carbon atoms is performed, and in the second and fourth stage polymerization, ethylene-brobylene copolymerization is performed. Alternatively, ethylene-propylene-boriene polymerization can be carried out. The number of polymerization stages (the number of n) may be selected as the optimal number to obtain the desired product, as in the gas phase multistage method, and the polymerization method may be either continuous polymerization method or discontinuous polymerization method. In the case of propylene homopolymerization or copolymerization of brobylene and alpha monoolefin having 4 to 30 carbon atoms, the ff! synthesis temperature is usually 0 to 200°C (preferably 60 to 100°C). range, and propylene pressure is usually 1-50 Kg/cm
Selected within the range of 2. In addition, in the case of ethylene-propylene copolymerization or ethylene-propylene-boriene copolymerization, the polymerization temperature is usually 0 to 200°C (preferably 40 to 200°C).
80°C) and the olefin pressure is usually between 1 and 50°C.
Selected within the range of Kg/cs2. In all of the above polymerizations, a reaction time of about 5 minutes to 10 hours is sufficient, and the molecular weight of the polymer can be adjusted by known means, for example, by adjusting the hydrogen concentration in the polymerization vessel. In the case of an ethylene-propylene copolymer, the ethylene unit content can be adjusted by adjusting the feed gas composition, and in the case of an ethylene-propylene-boriene copolymer, clause 7A of the polyene unit content is determined by adjusting the feed amount. This can be done by As the polyene monomer, the polyene f-nomer mentioned in the gas phase multi-stage method can be used. The above brobylene compositions (d) and (e) are composed of a polypropylene polymer (a) or a random copolymer (b) and an ethylene-propylene copolymer (C) or an ethylene-propylene copolymer (C). It can be prepared by blending a polyene copolymer (C°) using a known method (for example, dry blending or kneading). The polypropylene polymer (a) and the random copolymer (b) can be obtained by the gas phase one-stage polymerization method or the slurry one-stage polymerization method, and the ethylene-propylene copolymer (c) or Each of the ethylene-propylene-boriene copolymers (C°) can be obtained by known methods. Note that post-treatment after polymerization can be carried out by conventional methods. That is, in the gas-phase one-stage polymerization method or the gas-phase multi-stage polymerization method, after polymerization, the polymer powder extracted from the polymerization vessel contains
In order to remove unreacted olefins contained in this,
A stream of nitrogen or the like may be passed through. Further, if desired, it may be pelletized using an extruder, and at that time, a small amount of water, alcohol, etc. may be added to completely deactivate the catalyst. In addition, in the slurry one-stage polymerization method or slurry-multistage polymerization method, after polymerization, the monomer can be completely separated from the polymer derived from the polymerization vessel and then pelletized. (↓XV-Margin) The laminate of the invention contains the above-mentioned soft polypropylene in at least one material layer. In addition, other material layers are
It is preferable that at least one of a thermoplastic resin layer and a thermosetting resin layer is included. On the other hand, the other material layers are at least metal, rubber, cloth, paper, wood, cellophane, etc.
Alternatively, it may be formed from any one of leather. Which of these materials is used for the "other material layer" may be selected as appropriate depending on the use of the laminate. The thermoplastic resin constituting the "other material layer" may be appropriately selected depending on the use of the laminate to be manufactured, and is not particularly limited. Examples include styrenic polymers such as atactic structure boristyrene, isotactic structure boristyrene, syndiotactic structure boristyrene, AS resin, ABS resin, polyethylene terephthalate (PE), etc.
T). Examples include polyester resins such as polybutylene terephthalate (PBT), polycarbonate resins, polyphenylene sulfide resins (pps), and polyamide resins. In addition, polyphenylene oxide, boris sulfone. Polyether resins such as polyether sulfone, acrylic resins such as polyacrylic acid, polyacrylic acid ester, polymethyl methacrylate, polyethylene, polypropylene, polybutene,
Ethylene-alpha olefin copolymers such as poly-4-methylbentene-1, ethylene-propylene copolymer, ethylene-propylene-butene-1, ethylene-acrylic acid copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate Polyolefin resins such as copolymers, halogen-containing vinyl compound polymers such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene, polyoxymethylene, polyvinyl alcohol resins and their derivatives, ethylene-carboxylic anhydride copolymers Examples include ionomers, which are metal salt compounds. Among these, if high mechanical strength is required for the resulting resin laminate, polyester resin, polyamide resin, polycarbonate resin, polyolefin resin, or halogen-containing vinyl compound polymer should be selected as the thermoplastic resin. In addition, if gas barrier properties are important, polyester resins such as PET, polyamide resins, pps, polyvinyl alcohol resins and their derivatives, ethylene vinyl acetate, polyvinylidene chloride, etc. should be selected, and other materials with low melting points should be selected. By selecting a thermoplastic resin, a laminate with good heat sealability can be obtained. In particular, if low-temperature heat sealability is important, polypropylene (PP), PET, PBT, etc. should be selected. Also, from the perspective of maintaining sufficient flexibility,
Polyamide, ethylene-vinyl acetate copolymer (EVA)
, polyethylene (PE), polyvinyl chloride (PVC)
It is preferable to select Further, examples of the thermosetting resin constituting the "other material layer" include polyurethane, unsaturated polyester, epoxy, silicon, and phenol. Examples of metals constituting the "other material layer" include aluminum (AI) and iron (Fe), and examples of fabrics include woven fabrics, knitted fabrics, and nonwoven fabrics. From the viewpoint of placing importance on heat sealability, aluminum, cloth, and paper are suitable; when placing importance on flexibility, rubber is suitable. Figure 1 (a), (b). (c) is a sectional view showing an example of the structure of the laminate of the present invention. Figure (a) shows an example of a structure consisting of two layers: a soft polypropylene layer lOO and another material layer 200. As an example of this application, it is also possible to have a structure in which another material layer is superimposed on the other material layer 200. Figure (b) shows a structure in which a soft polypropylene layer 100 is superimposed on both sides of another material layer 200. As an example of this application, it is also possible to create a structure in which multiple layers of other materials are provided between two soft polypropylene layers. The figure (C) shows a structure in which another material layer Zoo, 300 is superimposed on both sides of the soft polypropylene layer 100. As an example of this application, it is also possible to have a structure in which multiple layers of other materials are stacked on both sides of the soft polypropylene layer lOO. Furthermore, one or more of the above examples may be combined. The thickness of the laminate is not particularly limited, but it is preferably 10 to 2000 μm in order to maintain flexibility.

There is also no particular limit to the thickness of the soft polypropylene layer, but in order to bring out the material of the same layer sufficiently, it is
It is preferable to set it within the ogm range. By the way, in manufacturing the laminate of the present invention, various methods can be considered depending on the form and use of the laminate, and conventional methods may be combined as appropriate depending on the situation. Specifically, the following manufacturing methods can be cited. That is, the following method can be cited as a method for manufacturing a laminate consisting of a soft polypropylene layer and a thermoplastic resin layer. The first method is to coextrude soft polypropylene (soft PP) and thermoplastic resin in multiple layers from a forming machine with a multilayer die to create a multilayer cast shaped film, or to perform multilayer inflation or shaping. be. At this time, in order to increase the adhesive strength of the living room, soft P was used as the third component.
It is also possible to provide an adhesive layer having affinity with each of the P and thermoplastic resin layers, or to mix an adhesive material in advance with either or both of the soft PP and the thermoplastic resin. In addition, when producing a multilayer cast or shaped film, the T-tie temperature should be 190 to 320°C, preferably 200°C.
It is preferable to set the cooling roll temperature to 90°C or less, and to set the take-up speed in the range of 5 to 130 m/min, preferably 30 to 130 m/min. In particular, if the cooling roll temperature is set to 90°C or less, a non-quality film can be obtained, and if the take-up speed and extrusion speed ratio, that is, the draft ratio, is set to 4 or less, a non-oriented raw sheet (film) can be obtained. It is suitable for stretching. The desired resin laminate can be obtained in this way or by subsequently carrying out a stretching treatment if necessary. When stretching the stretched multilayer film, the stretching method may be appropriately selected from uniaxial stretching, tubular monobiaxial stretching, sequential biaxial stretching, simultaneous two-wheel stretching, and the like. The conditions for this stretching process vary depending on the situation and may not be unambiguously determined, or the temperature is usually 80°C.
It is sufficient to set the above melting point or lower and set the stretching ratio to at least 3 times or more on at least one side. In addition, for this stretched multilayer film, it is preferable to perform heat treatment as a post-treatment to obtain sufficient dimensional stability.The heat treatment temperature at this time varies depending on the melting point and glass transition temperature of the film used, and is usually 80 to You just need to set it to ℃, and the processing time is 2 seconds to 2
It takes about 0 minutes. The second method is to prepare a soft PP film (stretched or unstretched) and a thermoplastic resin film (stretched or unstretched) separately in advance, and then laminate them. In this lamination, the surface of each film may be treated by corona treatment or ozone treatment, and an interlayer adhesive (for example, a tri-laminate adhesive such as a hardening type or urethane adhesive) may be used. It can also happen. Note that the press roll temperature during lamination is approximately 40 to 100°C, and the processing speed is appropriately 50 to 150 m/min.

The first and second methods can also be applied as a method for manufacturing a laminate comprising layers of materials other than the thermoplastic resin layer and a soft polypropylene layer. Now, we will individually explain which manufacturing method is suitable for which structure using examples. First, the coextrusion method that does not use adhesive
Suitable for laminating P and PP, ethylene-brobylene copolymer, polybutene l, ethylene-vinyl acetate copolymer, etc. Co-extrusion method using adhesive (carboxylic acid modified polypropylene etc.)
) etc. is suitable for lamination.

In the case of a laminate made of these materials, a method in which a film or sheet made of soft PP is laminated with a layer of another material coated with an adhesive is also suitable. In this case, use a urethane adhesive as the adhesive. The method of laminating other material layers after coextruding Soga PP and adhesive is suitable when using thermosetting resin, metal, paper, cloth, cellophane, rubber, wood, etc. as the other material layer. There is. In the above manufacturing method, the extrusion temperature is not uniquely determined depending on the type of material layer, but is usually 170 to 320"C, preferably 200"C.
The temperature is set at ~280℃. The laminate of the present invention described above is
The soft polypropylene layer has a welding temperature of approximately 143°C, a flexural modulus of approximately 3000 kg/c weight, and a heat resistance temperature of 140 to 165°C, all of which have good properties, so it has good low-temperature heat sealability and is flexible. Therefore, it is suitable for the following uses. Namely, this laminated layer is used as an outer layer or an intermediate layer of packaging materials used for general packaging, packaging of root vegetables, etc. If we use the material, we can provide packaging materials with excellent earthquake resistance (especially blocks), flexibility, and heat resistance.Specifically, homopolypropylene (H
PP). /Soft WPP/Random polypropylene (RPP
) or a laminate consisting of EVA, RPP/soft P
A laminate having a P/RPP structure is suitable for this packaging material. Furthermore, when used as the inner layer of packaging materials, it is possible to provide packaging materials with excellent low-temperature heat sealability and heat resistance. Specifically, laminates consisting of nylon (NY)/soft PP, ethylene-vinyl alcohol modified polymers (E
A laminate having a structure of VOH)/soft PP is suitable for this packaging material, and in particular, these can be used as wrap films and stretch films. Furthermore, a laminate of metal and soft PP can be used to cover steel plates or steel pipes and for the interior of automobiles, a laminate of cloth and soft PP can be used to make book covers with excellent flexibility and texture, and a laminate of cloth and soft PP can be used to make book covers with excellent texture. Bags, etc. can be manufactured by laminating with PP. [Example] A laminate was manufactured using homotype soft PP (soft Hoshichi PP) manufactured by the method described below.

(A) Production example of soft homobolypropylene (1) Preparation of fixed catalyst 20 ml of purified hebutane, Mg (
O E t ) 2 '4 g and phthalate di n
- Add 1.2 g of butyl, keep the inside of the system at 90'C, drop TiCl<4 ml without stirring, and then add more TiCl.
c-bun 4 111 m-bun was added and the temperature was raised to 110°C. After reacting for 2 hours at 110"C, it was washed with purified butane at 80"C.
15 m of water was added, and the reaction was further carried out at 110°C for 2 hours.

After the reaction was completed, the raw material was washed several times with purified heptane (Zoom) to obtain a solid catalyst (corresponding to solid catalyst (ii) in the gas phase method). (2> Preparation of solid extract In a pressure-resistant glass three-necked flask with a content of yi 2.51, which was sufficiently purged with nitrogen, 1.7 g of purified hebutane was added, AJJEt3
0.07 mol, Cyphenyldimethoxysilane (DPDM
S) 0.05 mmol and the catalyst fraction 12 of (1) above
Added 0g. The inside of the system was maintained at 30°C, propylene was continuously supplied while stirring, and the internal pressure was reduced to 0. 5 kg/c
It was kept at m2. After continuing this reaction for 1 hour, it was washed 5 times with purified butane 1M, and the solid component [solid component of the gas phase method]
equivalent to I)] was obtained. (3) A pressure-resistant autoclave made of stainless steel containing 20 g of gas-phase first-stage polymerized polypropylene powder was charged with A I E t : +3 mmol, 1-allyl-3,4-dimethoxybenzene (AD
MB) 0.15 mmol, diphenyldimethoxysilane (DPDMS) 0.23 mmol, and solid fraction (1) of the above (2) 100 mg (0.06 in terms of Ti atoms)
20 ml of a heptane solution containing 1 mmol) was added. After evacuating the system for 5 minutes, the hydrogen gas was evacuated to 0. 7 kg
/ cm” and the total pressure is 28 Kg/a.
Gas phase polymerization was carried out at 70°C for 1.7 hours while supplying propylene gas until the melt index (
MI) or 10g/10min soft polypropylene 640g
I got it. The boiling hebutane soluble content (HSP content) of this soft polypropylene is 46.8% by weight, and the intrinsic viscosity is 1.
It was 13 dl/g. In addition, boiling butane insoluble matter (
HIP content) is 53.2% by weight, and the intrinsic viscosity is 1.7
It was 4d sentences/g. Furthermore, in the bentat fraction by C-NMR, rr r r / 1 - m m
m m is 34.5%, and the melting peak temperature (T m ) measured by DSC is 158°C. The enthalpy of fusion (ΔH) measured by DSC is 58.2 J/g,
A domain structure was observed under transmission electron microscopy.

(B) Manufacturing conditions The manufacturing conditions for the laminate are as follows. The other material layers are homo PP (F-700N manufactured by Idemitsu Petrochemical Co., Ltd.).
(product name)) was used.

・Layer structure: Soft homo PP/Homo PP/Soft homo PP (thickness ratio 1/8/1) ・Film thickness: 30 pm/240 gm/30 lm ・Produced and used molding machine by co-extrusion method For soft homo PP : Screw diameter 20 mm Extruder homo PP: Screw diameter 30 mm Extruder multi-manifold use/forming conditions: Resin temperature 250"C/Extrusion rate Soft homo PP: 1.1 to 1.2 Kg/Hr Homo PP :9.5~9.5 Kg/Hr・Others: Chill roll temperature 35℃, air knife used, take-up speed 5~
The laminate manufactured at a speed of 5.5 m/min had a heat sealing temperature of 143°C and a heat resistance temperature of 145°C or higher, showing excellent properties in low-temperature heat sealability and heat resistance. Instead of the soft homo-PP of Example 1, a block-type soft PP (soft block PP) was produced by the following method.
A laminate was produced under the same conditions as in Example 1.

Example of Production of Soft Block Polypropylene After preparing the solid catalyst component and solid fraction A in the same manner as the above-mentioned soft homopolypropylene, the following procedure was carried out. (1) AuEt. 3 mmol, 1-
Allyl-3,4-dimethoxybenzene (ADMB) 0.
15 mmol, diphenyldimethoxysilane (DPDM
S) 0.23 mmol, and 100 mg of the solid component (I) prepared in Production Example 1 (1) and (2) above.
20 ml of heptane solution containing (0.06 mmol in terms of Ti atoms) was added. After evacuating the system for 5 minutes, hydrogen gas was introduced to 0.7 Kg/cm2, and gas phase polymerization was carried out at 70°C for 1.7 hours while supplying brobylene gas until the total pressure reached 28 Kg/cm2. Ta. (2)
Gas-phase second-stage polymerization After the reaction in (1) above is completed, the system is depressurized and exhausted, and hydrogen gas (0.5 kg/c) and ethylene-propylene mixed gas (molar ratio 1/4) are added. 10 kg/cm”
The gas phase polymerization was carried out at 50° C. for 1.4 hours.

810 g of soft polypropylene with a melt index (MI) of 4.4 g and 710 min was obtained. This flexible polypropylene consists of 81% by weight of polypropylene homopolymer and 39% by weight of ethylene-propylene copolymer, and the homopolymer has a boiling hebutane soluble content (HSP content) with an intrinsic viscosity of 1.13 db/g. 46.8% by weight and intrinsic viscosity of 1.74d
l/g boiling butane insoluble content (HIP content) 53.
2% by weight, and the bentad fraction by C-NMR is r r r r / 1 - mm m m
m or 34.5%, melting peak temperature measured by DSC (
Tm) was 158°C, the enthalpy of fusion (ΔH) measured by DSC was 58.2 J/g, and a domain structure was observed when observed with a transmission electron m* mirror. On the other hand, the ethylene unit content of the copolymer was 39 mol%, and the intrinsic viscosity was 1.77 dl/g. As a result of the above example, the heat sealing temperature was 143°C, similar to Example 1. #A laminate with a thermal temperature of 145°C or higher was able to be obtained.

1. A laminate was produced by laminating a layer of soft homo-PP (same as in Example 1) and nylon scraps using an adhesive. The layer structure is soft H7 PP/adhesive/nylon/adhesive/
It is a soft homopp (thickness ratio 1/0.5/8/0.5/1). In addition, for nylon, ηr (relative accuracy) = 3.75
6-nylon (manufactured by Ube Industries, Ltd.) was used, and carboxylic acid-modified polypropylene was used as the adhesive. The molding machine used was the same as in Example 1 (an extruder for adhesive was attached, a foot block and a multi-manifold were used. The molding temperature was 250°C, and the amount of nylon extruded was 1.1
．． 5-11. 8Kg/Hr. The throughput of carboxylic acid-modified polypropylene was 0. 6 Kg/Hr. The film thickness is 30 gm with the above cutting machine 715 gm
A laminate film of /2404m/30gm was obtained, and this was stretched to 3x3 with a table tenter to form a laminate film of 3lm/1.5pLm/27gm/1.5pm/3u.
The film thickness was set to Lm. This laminate film also had excellent heat resistance and oxygen impermeability, and exhibited properties suitable for use as a wrap film. Actual 0 raw 4 Soft homo PP (same as Example 1) layer and EVOH layer,
A laminate was fabricated by laminating layers using adhesive. The layer structure is soft homo PP/adhesive/EVOH/adhesive/
It is soft H7PP. As EVOH, EP-F (manufactured by Kuraray Co., Ltd.) with an ethylene content of 32 mol % was used, and the other conditions were the same as in Example 3. The stretched film had excellent oxygen impermeability and heat resistance, and exhibited properties suitable for use as a wrap film. A laminate was produced by laminating a layer of soft homo-PP (same as in Example 1) and an aluminum layer using an adhesive. The layer structure is soft homo-PP/adhesive/aluminum. For production, an adhesive extruder was attached to the soft PP extruder used in Example 1, and soft PP/adhesive = 30gm/
A 15 gm coextrusion was carried out, and a 15 μm thick aluminum foil was laminated thereon. A bag was formed by heat-sealing the inner layer of the resulting film as soft PP. The heat-sealing temperature at this time was 143°C, and the heat-resistant temperature was 145°C or higher, showing excellent low-temperature heat-sealability and heat resistance, and suitable characteristics for use in retort pouches, for example. [Effects of the Invention] As explained above, by mainly using soft polypropylene, the laminate of the present invention can have a welding temperature lower than conventional ones, for example, by 15 degrees Celsius, and also has improved flexibility and heat resistance. As a result, it has the effect of being able to be used in packaging materials, film materials, sheet materials, etc. for various purposes to improve their commercial value.

[Brief explanation of the drawing]

Figure 1(a). (b) and (c) are cross-sectional views each showing an example of the structure of the laminate of the present invention. Zoo: Soft polypropylene layer 200: Other material layer

Claims (3)

[Claims] (1) A laminate comprising a plurality of material layers, in which at least one material layer is mainly made of soft polypropylene. (2) The laminate according to claim 1, characterized in that the laminate includes a material layer made of at least one of a thermoplastic resin and a thermosetting resin. (3) The laminate according to claim 1 or 2, characterized in that the laminate includes a material layer made of at least one of metal, rubber, cloth, paper, wood, cellophane, or leather.