JP2003313234A - Construction material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a construction material having such excellent properties as damping properties, abrasion resistance, scuff resistance, and the like, and capable of retaining transparency and these physical properties even when it is highly filled with a filler or a flame retardant. <P>SOLUTION: This construction material is composed of a hydrogenated copolymer obtained by hydrogenating a copolymer consisting of a conjugated diene and a vinylaromatic compound, and the hydrogenated copolymer component (1) is specified as follows: (a) a content of the vinylaromatic compound in the hydrogenated copolymer is >50 wt.% and ≤90 wt.%; (b) a content of the block of the vinylaromatic compound in the hydrogenated copolymer is ≤40 wt.%; (c) a weight average molecular weight of the hydrogenated copolymer is 50,000-1,000,000; and (d) at least 75% of the double bonds based on the conjugated diene compound in the hydrogenated copolymer are hydrogenated, and the construction material is also composed of a composition compounded with the hydrogenated copolymer component (1), a thermoplastic resin and/or a rubbery polymer component (2) and further a filler and/or a flame retardant (3). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has physical properties such as excellent vibration damping property, abrasion resistance, and scratch resistance, and is transparent and has the above-mentioned physical properties even when a filler or a flame retardant is contained in a high concentration. The present invention relates to a building material capable of maintaining the above-mentioned properties, particularly a flooring material, a wall material, a ceiling material, and a sealing material composition.

[0002]

2. Description of the Related Art Conventionally, vinyl chloride resin has been widely used as a building material, particularly a floor material, a wall material, a ceiling material, and a sealing material. The vinyl chloride resin has a wide range of hardness and mechanical properties that can be set by adjusting the amounts of plasticizer and filler added, and provides a material with excellent flexibility, abrasion resistance, and scratch resistance. You can However, due to the weight reduction of materials and the concern that the incineration of the resin and the high load on the environment at the time of decomposition are high in recent years, there is an increasing demand for replacing the polyvinyl chloride-based material with another material. Examples of such alternative material candidates include olefin resins, ethylene-vinyl acetate copolymers, ethylene-acrylic acid ester copolymers, styrene block copolymers, and the like.

Of these, olefin resins such as ethylene-α-olefin copolymers have the problem that it is difficult to print or paint on the surface because their molecular structure is non-polar. It was Further, when a filler is added, the upper limit of the fillable ratio is low, and the dispersibility of the filler may be insufficient. In addition, ethylene-vinyl acetate copolymer has low heat resistance, and when vinyl acetate monomer remains in the product, it has a peculiar unpleasant odor, and the possibility of acetaldehyde generation due to the decomposition of residual vinyl acetate monomer. There were problems such as
Styrenic block copolymers and compositions thereof include styrene-butadiene-styrene block copolymers, styrene-
Typical isoprene-styrene block copolymers, which have a double bond in the molecule and have the drawbacks of low chemical resistance and weather resistance. Further, these block copolymers are hydrogenated (see, for example, Patent Document 1).
However, the production cost is high and the industrial application fields are limited. Further, all the polymers had a great difference from the physical properties such as the elastic modulus, abrasion resistance and scratch resistance of the polyvinyl chloride resin.

[Patent Document 1] Japanese Patent Laid-Open No. 2000-265035

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems and to have excellent strength, abrasion resistance, scratch resistance, vibration damping property, etc. It is an object of the present invention to provide a building material, particularly a flooring material, a wall material, a ceiling material, and a sealing material, which exhibits the above-mentioned properties and can maintain the transparency and the above-mentioned physical properties even when it contains a filler or a flame retardant at a high concentration.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have found that a conjugated diene and a vinyl aromatic compound having a specific vinyl aromatic compound content and a vinyl aromatic compound polymer block content within a specific range. A building material comprising a hydrogenated product of a copolymer with a compound or a composition containing the hydrogenated product,
In particular, they have found that the above problems can be solved by using a floor material, a wall material, a ceiling material, and a sealing material, and completed the present invention. That is, the present invention is [1] a building material comprising a hydrogenated copolymer, wherein the hydrogenated copolymer is a water obtained by adding hydrogen to a copolymer comprising a conjugated diene and a vinyl aromatic compound. Is an addition copolymer,
And (a) the content of the vinyl aromatic compound in the hydrogenated copolymer is more than 50% by weight and 90% by weight or less, and (b) the block (H) of the vinyl aromatic compound in the hydrogenated copolymer is contained. 40% by weight or less, (c) the weight average molecular weight of the hydrogenated copolymer is 50,000 to 1,000,000, and (d) 75% or more of the double bond based on the conjugated diene compound in the hydrogenated copolymer is water. A building material characterized by being a hydrogenated copolymer being added,

[2] A building material comprising a composition comprising the following hydrogenated copolymer component (1) and a thermoplastic resin and / or rubber-like polymer component (2): The addition copolymer is a hydrogenation copolymer obtained by adding hydrogen to a copolymer comprising a conjugated diene and a vinyl aromatic compound, and (a) a vinyl aromatic compound in the hydrogenation copolymer. The content is more than 50% by weight and 90% by weight or less, (b) the block (H) content of the vinyl aromatic compound in the hydrogenated copolymer is 40% by weight or less, and (c) the hydrogenated copolymer. 5 to 95 parts by weight of hydrogenated copolymer having a weight average molecular weight of 50,000 to 1,000,000 and (d) 75% or more of double bonds based on the conjugated diene compound in the hydrogenated copolymer are hydrogenated. , (2) 5 to 95 parts by weight of a thermoplastic resin and / or a rubber-like polymer, Building materials characterized in that it comprises,

[3] A building material comprising a composition comprising the following hydrogenated copolymer component (1) and a filler and / or flame retardant component (3), wherein (1) the hydrogenated copolymer weight The combined product is a hydrogenated copolymer obtained by adding hydrogen to a copolymer composed of a conjugated diene and a vinyl aromatic compound, and (a) the content of the vinyl aromatic compound in the hydrogenated copolymer is 50% by weight
90% by weight or less, (b) the block (H) content of the vinyl aromatic compound in the hydrogenated copolymer is 40% by weight or less, and (c) the weight average molecular weight of the hydrogenated copolymer is 50,000. -10
0,000, (d) 5 to 95 parts by weight of a hydrogenated copolymer in which 75% or more of the double bonds based on the conjugated diene compound in the hydrogenated copolymer are hydrogenated, (3) a filler, and Alternatively, a building material comprising a composition containing 5 parts by weight to 95 parts by weight of a flame retardant,

[4] From a composition comprising the following hydrogenated copolymer component (1), thermoplastic resin and / or rubbery polymer component (2), filler and / or flame retardant component (3) (1) The hydrogenated copolymer is a hydrogenated copolymer obtained by adding hydrogen to a copolymer composed of a conjugated diene and a vinyl aromatic compound, and (a) The content of the vinyl aromatic compound in the hydrogenated copolymer is more than 50% by weight and 90% by weight or less, and (b) the block (H) content of the vinyl aromatic compound in the hydrogenated copolymer is 40% by weight. % Or less, the weight average molecular weight of the (c) hydrogenated copolymer is 50,000 to 10
0,000, (d) 5% to 95% by weight of a hydrogenated copolymer in which 75% or more of the double bond based on the conjugated diene compound in the hydrogenated copolymer is hydrogenated, (2) thermoplastic (3) Filler and / or flame retardant 5 per 5 parts by weight to 95 parts by weight of the total amount of component (1) + component (2) consisting of 5% by weight to 95% by weight of resin and / or rubbery polymer. The present invention provides a building material, which is characterized by comprising a composition containing 1 to 95 parts by weight.

The present invention will be described in detail below. The hydrogenated copolymer of the component (1) of the present invention is a hydrogenated product of a copolymer composed of a conjugated diene and a vinyl aromatic compound. In the present invention, the content of the vinyl aromatic compound in the hydrogenated copolymer is more than 50% by weight and 90% by weight or less, preferably 60% by weight or less.
More than 88% by weight, more preferably 62-
It is 86% by weight. It is necessary to use a vinyl aromatic compound having a content within the range specified in the present invention in order to obtain a building material excellent in vibration damping property, abrasion resistance, scratch resistance and the like. In the present invention, the content of the vinyl aromatic compound in the hydrogenated copolymer may be grasped by the content of the vinyl aromatic compound in the copolymer before hydrogenation. In the hydrogenated copolymer used in the present invention, the block (H) content of the vinyl aromatic compound is 40% by weight or less, preferably 3%.
-40% by weight, more preferably 5-35% by weight.

In order to obtain the building material of the present invention, when more flexible one is preferred, the block (H) content of the vinyl aromatic compound is less than 10% by weight, preferably less than 8% by weight, more preferably Is recommended to be less than 5% by weight. In addition, in obtaining the building material of the present invention, when a block copolymer having excellent blocking resistance is preferred as the hydrogenated copolymer, the block (H) content of the vinyl aromatic compound is 10
It is recommended to be -40% by weight, preferably 13-37% by weight, more preferably 15-35% by weight. When the block content (H) of the vinyl aromatic compound exceeds 40% by weight, scratch resistance and vibration damping property are poor, which is not preferable. The block (H) content of vinyl aromatic compounds is measured by a method of oxidatively decomposing a copolymer before hydrogenation with tert-butyl hydroperoxide using osmium tetroxide as a catalyst (IMKOLTHOFF, et al., J. Polym. .Sci.
1,429 (1946)), using the weight of the vinyl aromatic hydrocarbon block component (excluding the vinyl aromatic hydrocarbon polymer component having an average degree of polymerization of about 30 or less). Then, it can be obtained from the following equation. Block (H) content of vinyl aromatic hydrocarbon (% by weight) = (weight of block (H) of vinyl aromatic hydrocarbon in copolymer before hydrogenation / weight of copolymer before hydrogenation) × 100

The content of the vinyl aromatic polymer block (H) in the hydrogenated copolymer is determined by using a nuclear magnetic resonance apparatus (NMR) (Y. Tanaka,
et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (19
The method described in 81)) can be directly measured, but in the present invention, the value obtained by the osmium tetroxide decomposition method described above is the content of the vinyl aromatic polymer block (H). Content of vinyl aromatic polymer block (H) of copolymer before hydrogenation measured by osmium tetroxide decomposition method (referred to as "Os value") and copolymerization weight after hydrogenation measured by NMR method Between the content of the combined vinyl aromatic polymer block (H) (referred to as “Ns value”),
There is a correlation. As a result of studying various copolymers having different vinyl aromatic polymer block (H) contents, the relationship can be expressed by the following formula. Os value = -0.01
2 (Ns value) 2 + 1.8 (Ns value) -13.0

Therefore, when the content of the vinyl aromatic polymer block (H) in the polymer after hydrogenation is determined by the NMR method in the present invention, the Ns value is converted into the Os value based on the above formula. , And the content of the vinyl aromatic polymer block (H). In the present invention, the block ratio of the vinyl aromatic compound in the hydrogenated copolymer (the block ratio means the ratio of the block content of the vinyl aromatic compound to the total amount of the vinyl aromatic compound in the copolymer). Is preferably less than 50% by weight, more preferably 20% by weight or less, and further preferably 18% by weight or less in order to obtain a composition having better flexibility.

The weight average molecular weight of the hydrogenated copolymer used in the present invention is 5 to 1,000,000, preferably 100,000 to 800,000, and more preferably 13 to 500,000. When the hydrogenated copolymer having a block ratio of the vinyl aromatic compound of 10 to 40% by weight is used, the weight average molecular weight thereof is more than 100,000 and less than 500,000, preferably 130,000 to 400,000, more preferably 150,000. ~ 300,000 is recommended. Weight average molecular weight is 5
If it is less than 10,000, the mechanical strength and heat resistance will be poor, and 100
When it exceeds 10,000, it is not preferable because the moldability is poor.
In the present invention, the molecular weight distribution of the hydrogenated copolymer is preferably 1.5 to 5.0, more preferably 1.6 to 4.5, still more preferably 1.8 to 4 from the viewpoint of molding processability. Is recommended. The hydrogenated copolymer used in the present invention is a hydrogenated product of a copolymer composed of a conjugated diene and a vinyl aromatic compound, and contains 75% or more of double bonds based on the conjugated diene compound in the copolymer, preferably 85% or more, more preferably 90% or more, and particularly preferably 92% or more are hydrogenated. When the hydrogenation rate is less than 75%, the weather resistance and heat stability are poor.

The hydrogenated copolymer of the present invention is -5 in the DSC chart obtained by differential scanning calorimetry (DSC).
It is preferable that the hydrogenated product has substantially no crystallization peak in the range of 0 to 100 ° C. Here, "-50
The crystallization peak substantially does not exist in the range of up to 100 ° C. ”means that even if a peak due to crystallization does not appear in this temperature range or a peak due to crystallization is observed, the crystallization peak It has a crystallization peak calorie of less than 3 J / g, preferably less than 2 J / g, more preferably less than 1 J / g, and particularly preferably has no crystallization peak calorie. The hydrogenated copolymer having a crystallization peak becomes a polymer having extremely poor flexibility,
It is not suitable for the purpose of the present invention to develop into applications where a soft vinyl chloride resin is used. -50 as above
In order to obtain a hydrogenated copolymer having substantially no crystallization peak in the range of -100 ° C, the polymerization reaction should be carried out under the conditions described below using the vinyl bond amount modifier described below. The non-hydrogenated copolymer obtained by the above may be used.

In the present invention, the structure of the hydrogenated copolymer is not particularly limited, and any structure can be used.
Particularly recommended is a hydrogenated product of a copolymer having at least one structure selected from the following general formulas. The hydrogenated copolymer used in the present invention may be any mixture of hydrogenated copolymers having a structure represented by the following general formula. Further, a vinyl aromatic compound polymer may be mixed with the hydrogenated copolymer. S S-H S-H-S (S-H) m-X (S-H) n-X- (H) p (where S is a random copolymer block of a conjugated diene and a vinyl aromatic compound) And H is a vinyl aromatic compound polymer block, m is an integer of 2 or more, and n is
And p are integers of 1 or more. X represents a coupling agent residue. ) In the general formula, even if the vinyl aromatic hydrocarbons in the random copolymer block S are evenly distributed,
Alternatively, it may be distributed in a taper shape. Further, in the copolymer block S, a plurality of portions in which vinyl aromatic hydrocarbons are uniformly distributed and / or a plurality of portions in which taper distribution is formed may coexist. Further, m is an integer of 2 or more, preferably 2 to 10, and n and p are 1 or more, preferably an integer of 1 to 10.

In the present invention, the difference between the maximum value and the minimum value of the vinyl bond content in the copolymer chain before hydrogenation is less than 10%, preferably 8% or less, more preferably 6% or less. Is recommended. The vinyl bonds in the copolymer chain may be evenly distributed or tapered. Here, the difference between the maximum value and the minimum value of the vinyl bond content is the difference between the maximum value and the minimum value of the vinyl bond content determined by the polymerization conditions, that is, the type and amount of the vinyl amount modifier and the polymerization temperature. is there. The difference between the maximum value and the minimum value of the vinyl bond content in the conjugated diene polymer chain can be controlled by, for example, the polymerization temperature during the polymerization of the conjugated diene or the copolymerization of the conjugated diene and the vinyl aromatic compound. For a given type and amount of vinyl modifier, such as a tertiary amine compound or ether compound, the vinyl bond content incorporated into the polymer chain during polymerization depends on the polymerization temperature. Therefore, the polymer polymerized isothermally becomes a polymer in which vinyl bonds are uniformly distributed. On the other hand, a polymer polymerized at elevated temperature has a high vinyl bond content in the initial stage (polymerization at low temperature) and a low vinyl bond content in the latter half (polymerization at high temperature), and thus has a difference in vinyl bond content. . By adding hydrogen to the copolymer having such a structure, a hydrogenated copolymer having a specific structure can be obtained.

In the present invention, the content of the vinyl aromatic compound can be known by using an ultraviolet spectrophotometer. Further, the content of the vinyl aromatic compound polymer block can be known by the above-mentioned KOLTHOFF method or the like.
The vinyl bond content based on the conjugated diene in the copolymer before hydrogenation can be known using an infrared spectrophotometer (Hampton method). The hydrogenation rate of the hydrogenated copolymer can be known by using a nuclear magnetic resonance apparatus (NMR) or the like. In addition, in the present invention, the molecular weight of the hydrogenated copolymer is measured by gel permeation chromatography (GPC), and the molecular weight of the peak of the chromatogram is determined by measuring the standard curve of a commercially available polystyrene (standard curve). It is the weight average molecular weight obtained by using (prepared using the peak molecular weight of polystyrene). Similarly, the molecular weight distribution of the hydrogenated copolymer can be determined from the measurement by GPC.

In the present invention, the conjugated diene is a diolefin having a pair of conjugated double bonds, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene) and 2,3-dimethyl-1. , 3-Butadiene, 1,3
-Pentadiene, 2-methyl-1,3-pentadiene,
1,3-hexadiene and the like, but particularly common ones include 1,3-butadiene and isoprene. These may be used alone or in combination of two or more. Examples of vinyl aromatic compounds include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl- Examples thereof include p-aminoethylstyrene, and these may be used alone or in combination of two or more.

In the present invention, the microstructure of the conjugated diene moiety (cis, trans,
The ratio of vinyl) can be arbitrarily changed by using a polar compound described later and is not particularly limited. Generally, when 1,3-butadiene is used as the conjugated diene, the 1,2-vinyl bond content is 5 to 80%, preferably 10%.
-60%, when isoprene is used as the conjugated diene or when 1,3-butadiene and isoprene are used in combination, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is generally 3 to 75%, It is recommended to be preferably 5 to 60%. In the present invention, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (however, when 1,3-butadiene is used as the conjugated diene,
2-vinyl bond amount) is hereinafter referred to as vinyl bond. In the present invention, the copolymer before hydrogenation is obtained, for example, by anion living polymerization using an initiator such as an organic alkali metal compound in a hydrocarbon solvent. Examples of the hydrocarbon solvent include n-butane, isobutane, n-pentane, n
Aliphatic hydrocarbons such as hexane, n-heptane and n-octane, alicyclic hydrocarbons such as cyclohexane, cycloheptane and methylcycloheptane, and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene Is.

As the initiator, an aliphatic hydrocarbon alkali metal compound, an aromatic hydrocarbon alkali metal compound, which is generally known to have anionic polymerization activity for conjugated diene compounds and vinyl aromatic compounds, Organic amino alkali metal compounds and the like are included, and the alkali metal is lithium, sodium, potassium, or the like. Suitable organic alkali metal compounds are aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms, 1
A compound containing one lithium in the molecule, a dilithium compound containing a plurality of lithium in one molecule, a trilithium compound, and a tetralithium compound are included. Specifically, n-
Propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, n-hexyl lithium, benzyl lithium,
Examples thereof include reaction products of phenyllithium, tolyllithium, diisopropenylbenzene and sec-butyllithium, and further reaction products of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene. Further, 1- (t-butoxy) propyllithium disclosed in US Pat. No. 5,708,092 and a lithium compound having 1 to several molecules of isoprene monomer inserted therein to improve its solubility, British Patent 2 , 241,239
1- (t-butyldimethylsiloxy) hexyllithium and other siloxy group-containing alkyllithiums disclosed in US Pat. No. 5,527,753, amino group-containing alkyllithiums disclosed in US Pat. No. 5,527,753, diisopropylamide Amino lithiums such as lithium and hexamethyldisilazide lithium can also be used.

In the present invention, when a conjugated diene compound and a vinyl aromatic compound are copolymerized with an organic alkali metal compound as a polymerization initiator, a vinyl bond (1, 2, or 3, resulting from the conjugated diene compound incorporated in the polymer is obtained. A tertiary amine compound or an ether compound may be added as an adjusting agent in order to adjust the content of (4 bonds) and the random copolymerizability of the conjugated diene compound and the vinyl aromatic compound. The tertiary amine compound is represented by the general formula R ¹ R ² R ³ N (wherein R ¹ , R ² and R ³ are hydrocarbon groups having 1 to 20 carbon atoms or hydrocarbon groups having a tertiary amino group). Is a compound of. For example, trimethylamine, triethylamine, tributylamine, N, N
-Dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetraethylethylenediamine, 1,2-dipiperidinoethane , Trimethylaminoethylpiperazine, N, N, N ', N ", N"
-Pentamethylethylenetriamine, N, N'-dioctyl-p-phenylenediamine and the like.

The ether compound is selected from linear ether compounds and cyclic ether compounds, and the linear ether compound is dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, etc. And ethylene glycol dialkyl ether compounds, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and other diethylene glycol dialkyl ether compounds. Further, as the cyclic ether compound, tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane,
2,2-bis (2-oxolanyl) propane, an alkyl ether of furfuryl alcohol and the like can be mentioned.

In the present invention, the method of copolymerizing the conjugated diene compound and the vinyl aromatic compound using an organic alkali metal compound as a polymerization initiator may be batch polymerization, continuous polymerization, or a combination thereof. Good. In particular, a continuous polymerization method is recommended in order to adjust the molecular weight distribution within a preferable appropriate range. The polymerization temperature is generally 0 ° C to 180 ° C, preferably 30 ° C to 150 ° C. The time required for the polymerization varies depending on the conditions, but is usually within 48 hours, and particularly preferably 0.1 to 10 hours. The polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as it is within the range of the above-mentioned polymerization temperature and is a pressure sufficient to maintain the monomer and the solvent in the liquid phase. Further, it is necessary to take care so that impurities such as water, oxygen, carbon dioxide gas, etc. which inactivate the catalyst and the living polymer are not mixed in the polymerization system.

In the present invention, at the end of the polymerization, bifunctionality is obtained.
Add the required amount of the above coupling agent and
You can respond. As a bifunctional coupling agent
Any known one may be used without any particular limitation. example
For example, dimethyldichlorosilane, dimethyldibromosilane
Dihalogen compounds such as, methyl benzoate, ethyl benzoate
Acid, such as phenol, phenyl benzoate, and phthalates.
Tellers and the like can be mentioned. In addition, a trifunctional or higher polyfunctional cup
As the pulling agent, any known one may be used.
Not determined. For example, trihydric or higher polyalcohols,
Poxylated soybean oil, diglycidyl bisphenol A, 1,
3-bis (N, N'-diglycidylaminomethyl) siku
Polyvalent epoxy compounds such as rohexane, general formula R_4-nSi
X_n(However, R is a hydrocarbon group having 1 to 20 carbon atoms, X is
Is a halogen, and n is an integer of 3 to 4)
Silicon rogenide compounds, such as methylsilyl trichloride
, T-butylsilyl trichloride, silicon tetrachloride and
General formula R such as bromide _4-nSnX_n(However,
R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, n
Represents an integer of 3 to 4)
Such as methyltin trichloride, t-butyltin trichloride
Examples include polyvalent halogen compounds such as chloride and tin tetrachloride.
It Dimethyl carbonate or diethyl carbonate can also be used.

In the present invention, as the copolymer, a terminal-modified copolymer having a polar group-containing atomic group bonded to at least one polymer chain end of the polymer can be used. As the polar group-containing atomic group, for example, hydroxyl group, carboxyl group, carbonyl group, thiocarbonyl group, acid halide group, acid anhydride group, carboxylic acid group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group , Amide group, sulfonic acid group, sulfonic acid ester group,
Phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate group, silicon halide group, silanol group,
An atomic group containing at least one polar group selected from an alkoxysilicon group, a tin halide group, an alkoxytin group, a phenyltin group and the like can be mentioned. The terminal-modified copolymer is obtained by reacting a compound having these polar group-containing atomic groups at the end of the polymerization of the copolymer. As the compound having a polar group-containing atomic group, specifically, a terminal modification treatment agent described in JP-B-4-39495 can be used.

By hydrogenating the copolymer obtained above, the hydrogenated copolymer used in the present invention can be obtained.
The hydrogenation catalyst is not particularly limited, and conventionally known metals (1) such as Ni, Pt, Pd and Ru are carbon,
A supported heterogeneous hydrogenation catalyst supported on silica, alumina, diatomaceous earth, etc., (2) Organic acid salts such as Ni, Co, Fe and Cr, or transition metal salts such as acetylacetone salts and reducing agents such as organic aluminum. And a so-called Ziegler type hydrogenation catalyst, and (3) a homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Ti, Ru, Rh and Zr. Specific hydrogenation catalysts include JP-B-42-8704, JP-B-43-6636,
Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-39700, Japanese Patent Publication No. 1-53851, Japanese Patent Publication No. 2-904.
The hydrogenation catalyst described in Japanese Patent No. 1 can be used. Preferred hydrogenation catalysts include mixtures with titanocene compounds and / or reducing organometallic compounds.

As the titanocene compound, Japanese Patent Application Laid-Open No. 8-1
The compounds described in Japanese Patent Publication No. 09219 can be used,
Specific examples include at least one or more ligands having a (substituted) cyclopentadienyl skeleton, indenyl skeleton, or fluorenyl skeleton such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Compounds.
Further, as the reducing organic metal compound, an organic alkali metal compound such as organic lithium, an organic magnesium compound,
Examples thereof include organic aluminum compounds, organic boron compounds and organic zinc compounds. In the present invention, the hydrogenation reaction is generally 0 to 200 ° C, more preferably 30 to 15 ° C.
It is carried out in the temperature range of 0 ° C. The pressure of hydrogen used in the hydrogenation reaction is recommended to be 0.1 to 15 MPa, preferably 0.2 to 10 MPa, more preferably 0.3 to 5 MPa. The hydrogenation reaction time is usually 3 minutes to 10 hours,
It is preferably 10 minutes to 5 hours. The hydrogenation reaction can be used as a batch process, a continuous process, or a combination thereof.

The hydrogenated copolymer solution thus obtained can be separated from the solution by removing the catalyst residue if necessary. As a method for separating the solvent, for example, a method in which a polar solvent which is a poor solvent for the hydrogenated copolymer such as acetone or alcohol is added to the reaction solution after hydrogenation to precipitate and recover the polymer, and the reaction solution is stirred Examples thereof include a method in which the solvent is removed by steam stripping to remove the solvent, and a method in which the polymer solution is directly heated to distill off the solvent. still,
The hydrogenated copolymer of the present invention includes various phenolic stabilizers,
Stabilizers such as phosphorus-based stabilizers, sulfur-based stabilizers, and amine-based stabilizers can be added. The hydrogenated copolymer used in the present invention is an α, β-unsaturated carboxylic acid or derivative thereof,
For example, it may be modified with its anhydride, esterified product, amidated product, or imidized product. Specific examples of the α, β-unsaturated carboxylic acid or its derivative include maleic anhydride,
Maleic anhydride imide, acrylic acid or its ester,
Examples thereof include methacrylic acid or its ester, endo-cis-bicyclo [2,2,1] -5-heptene-2,3-dicarboxylic acid or its anhydride. The addition amount of the α, β-unsaturated carboxylic acid or its derivative is the hydrogenated polymer 10
It is generally 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 0 parts by weight.

Next, the thermoplastic resin or the rubber-like polymer of the component (2) in the present invention is not particularly limited, but the following can be mentioned as examples. As the thermoplastic resin of the component (2), a block copolymer resin of a conjugated diene compound and a vinyl aromatic compound and its hydrogenated product (however, different from the hydrogenated copolymer <component (1)> of the present invention) ), Polymers of said vinyl aromatic compounds, said vinyl aromatic compounds and other vinyl monomers such as ethylene, propylene, butylene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid esters such as acrylic acid and acrylmethyl. , Methacrylic acid and methacrylic acid esters such as methyl methacrylate, copolymer resins with acrylonitrile and methacrylonitrile, rubber-modified styrene resins (HIPS), acrylonitrile-butadiene-styrene copolymer resins (AB
S), methacrylic acid ester-butadiene-styrene copolymer resin (MBS), polyethylene, a copolymer of ethylene containing 50% by weight or more of ethylene and another monomer copolymerizable therewith, for example, ethylene-propylene copolymer. Polymer, ethylene-butylene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer and its hydrolyzate, ethylene-
50% of polyethylene resin such as acrylic acid ionomer and chlorinated polyethylene, polypropylene, propylene
Copolymers of propylene containing at least wt% and other monomers copolymerizable therewith, for example, propylene-ethylene copolymers, polypropylene-based resins such as propylene-ethyl acrylate copolymer and chlorinated polypropylene, ethylene -Cyclic olefin resin such as norbornene resin,
Polybutene resins, polyvinyl chloride resins, polyvinyl acetate resins and their hydrolysates, polymers of acrylic acid and its esters and amides, polyacrylate resins, polymers of acrylonitrile and / or methacrylonitrile, and these 50% by weight of acrylonitrile-based monomer
Nitrile resin which is a copolymer with other copolymerizable monomer contained above, nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, nylon-12, nylon-6 nylon-12 Polyamide-based resins such as copolymers, polyester-based resins, thermoplastic polyurethane-based resins, polycarbonate-based polymers such as poly-4,4'-dioxydiphenyl-2,2'-propane carbonate, polyether sulfone and polyallyl Thermoplastic polysulfone such as sulfone, polyoxymethylene-based resin, polyphenylene ether-based resin such as poly (2,6-dimethyl-1,4-phenylene) ether,
Polyphenylene sulfide resins such as polyphenylene sulfide and poly 4,4′-diphenylene sulfide,
Polyarylate resin, polyetherketone polymer or copolymer, polyketone resin, fluorine resin, polyoxybenzoyl polymer, polyimide resin, polybutadiene resin such as 1,2-polybutadiene, trans polybutadiene, etc. . The number average molecular weight of these thermoplastic resins is generally 1,000 or more, preferably 5,000 to
It is 5,000,000, and more preferably 10,000 to 1,000,000. Particularly preferable examples of the thermoplastic resin as the component (2) are styrene-based resins, ethylene-based and propylene-based copolymers.

The blending amount of the thermoplastic resin of the component (2) is 5 to 95% by weight based on the hydrogenated copolymer of the component (1),
It is preferably 5 to 90% by weight, more preferably 5 to 80% by weight. Although it depends on the rigidity and hardness of the target composition, if the content of the component (2) exceeds 95% by weight, impact resistance, vibration damping property and the like of the obtained composition are deteriorated, which is not preferable. As the rubber-like polymer of the component (2), butadiene rubber and its hydrogenated product, styrene-butadiene rubber and its hydrogenated product (however, different from the hydrogenated copolymer <component (1)> of the present invention) , Isoprene rubber, acrylonitrile-butadiene rubber and hydrogenated products thereof, chloroprene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, ethylene-octene rubber, and other olefin elastomers. , Butyl rubber, acrylic rubber, fluorine rubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylic acid ester-conjugated diene copolymer rubber, urethane rubber, polysulfide rubber, styrene-butadiene block copolymer polymerization Examples thereof include styrene-based elastomers such as polymers and hydrogenated products thereof, styrene-isoprene block copolymers and hydrogenated products thereof, and natural rubber. These rubbery polymers may be modified rubbers having functional groups. Particularly preferred as the rubber-like polymer of the component (2) are styrene-based elastomers and olefin-based elastomers.

The amount of the rubber-like polymer as the component (2) is 5 to 95% by weight based on the hydrogenated copolymer as the component (1).
It is preferably 5 to 90% by weight, more preferably 5 to 80% by weight. If the compounding amount of the component (2) exceeds 95% by weight, abrasion resistance and scratch resistance of the obtained composition are deteriorated, which is not preferable. Further, two or more kinds of these thermoplastic resins and rubber-like polymers may be used in combination, if necessary. The combination is not particularly limited, and may be the same as the thermoplastic resin component or the rubber-like polymer component, or may be the combination of the thermoplastic resin and the rubber-like polymer.

Next, the filler and the flame retardant of the component (3) of the present invention are not particularly limited as long as they are those generally used for compounding a thermoplastic resin or a rubber-like polymer. Examples of the filler of the component (3) include silica, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide,
Calcium sulfate, barium sulfate, carbon black, glass fiber, glass beads, glass balloons, glass flakes, graphite, titanium oxide, potassium titanate whiskers, carbon fiber, alumina, kaolin clay, silicic acid, calcium silicate, quartz, mica, Examples thereof include inorganic fillers such as talc, clay, zirconia, potassium titanate, alumina and metal particles, and organic fillers such as wood chips, wood powder and pulp. The shape is not particularly limited, such as scaly, spherical, granular, powder, and irregular shape. These can be used alone or in combination.

Next, examples of flame retardants include halogen-based flame-retardants mainly containing bromine compounds, phosphorus-based flame-retardants mainly containing aromatic compounds, and inorganic-based flame retardants mainly containing metal hydroxides. Flame retardants that are substantially free of halogen are preferred.
Examples of phosphorus flame retardants include triphenyl phosphate, tricresyl phosphate, trixylenol phosphate, cresyl diphenyl phosphate, and the like. Examples of the inorganic flame retardant include metal hydroxides such as magnesium hydroxide, aluminum hydroxide and calcium hydroxide, metal oxides such as zinc borate and barium borate, other calcium carbonate, clay, basic magnesium carbonate and hydrotalcite. Etc., and a water-containing metal compound etc. can be mainly illustrated. In the present invention, among the above flame retardants, a metal hydroxide such as magnesium hydroxide is preferable from the viewpoint of improving flame retardancy. Note that the above-mentioned flame retardants include so-called flame retardant auxiliaries, which have a low flame retardancy-developing effect by themselves, but exhibit synergistically superior effects when used in combination with other flame retardants. As the filler and flame retardant of the component (3), a type in which surface treatment is performed in advance with a surface treatment agent such as a silane coupling agent can be used.

The amount of the filler or flame retardant as the component (3) added is 5 to 95% by weight, preferably 10 to 80% by weight, more preferably 20 to 70% by weight, based on the whole composition. is there. If the blending amount of the component (3) exceeds 95% by weight, the processability and mechanical strength of the obtained composition are deteriorated, which is not preferable. If necessary, two or more kinds of these fillers and flame retardants may be used in combination. The combination is not particularly limited, and it may be the same as the filler component, the same as the flame retardant component, or a combination of the filler and the flame retardant.

If desired, the building material of the present invention may contain any additive. The kind of the additive is not particularly limited as long as it is generally used for blending the thermoplastic resin and the rubber-like polymer. For example, pigments and colorants such as carbon black and titanium oxide, stearic acid, behenic acid, zinc stearate, calcium stearate,
Lubricants such as magnesium stearate and ethylene bis-stearamide, mold release agents, organic polysiloxanes, phthalic acid ester-based and adipic acid ester compounds, fatty acid ester-based compounds such as azelaic acid ester compounds, plasticizers such as mineral oil, hindered Phenol-based antioxidants, antioxidants such as phosphorus-based heat stabilizers, hindered amine-based light stabilizers, benzotriazole-based UV absorbers, antistatic agents,
Examples of the reinforcing agent include organic fibers, glass fibers, carbon fibers, metal whiskers, other additives, and mixtures thereof.

The building material of the present invention can be crosslinked, if desired. Examples of the cross-linking method include a chemical method by adding a cross-linking agent such as peroxide and sulfur and, if necessary, a co-cross-linking agent, and a physical cross-linking method by electron beam, radiation and the like. As a cross-linking process, a static method,
A dynamic vulcanization method etc. can be illustrated. Examples of the cross-linking agent include organic peroxides, sulfur, phenol-based, isocyanate-based, thiuram-based, morpholine disulfide and the like. These are cross-linking aids such as stearic acid, oleic acid, zinc stearate and zinc oxide. , A co-crosslinking agent, a vulcanization accelerator and the like can be used in combination. Examples of the organic peroxide crosslinking agent include hydroperoxide, dialkyl peroxide, diallyl peroxide, diacyl peroxide, peroxy ester, ketone peroxide and the like.

The method for producing the building material or the composition constituting the building material of the present invention is not particularly limited,
Known methods can be used. For example, it is possible to perform dry blending with various mixers, such as a Banbury mixer, a single screw extruder, a twin screw extruder,
A melt-kneading method using a general kneader such as a kneader, a multi-screw extruder, or a roll, a method of dissolving or dispersing and mixing each component, and then heating and removing the solvent are used. In the present invention, the melt mixing method using an extruder is preferable from the viewpoint of productivity and good kneading property. The shape of the obtained building material or composition constituting the building material is not particularly limited, but pellets,
Examples thereof include a sheet shape, a strand shape, and a chip shape. Alternatively, after melt-kneading, a molded product can be directly produced.

The building material of the present invention is a sheet, a film,
It can be used as a wide variety of molded products such as injection molded products of various shapes, hollow molded products, pressure molded products, vacuum molded products, extrusion molded products. Further, when a foamed molded article is obtained as the building material of the present invention, the methods applicable to the present invention include a chemical method, a physical method, etc., and chemical foaming such as an inorganic foaming agent and an organic foaming agent, respectively. Bubbles can be distributed inside the material by adding a foaming agent such as an agent or a physical foaming agent. By using a foam material, weight reduction, flexibility improvement, design improvement, etc. can be achieved. Examples of the inorganic foaming agent include sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, azide compound, sodium borohydride, metal powder and the like.

As the organic foaming agent, azodicarbonamide, azobisformamide, azobisisobutyronitrile, barium azodicarboxylate, N, N'-dinitrosopentamethylenetetramine, N, N'-dinitroso-
N, N'-dimethylterephthalamide, benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide,
p, p'-oxybisbenzenesulfonyl hydrazide,
Examples thereof include p-toluenesulfonyl semicarbazide. Physical blowing agents include hydrocarbons such as pentane, butane and hexane, halogenated hydrocarbons such as methyl chloride and methylene chloride, gases such as nitrogen and air, trichlorofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane and chloro. Difluoroethane,
Examples thereof include fluorinated hydrocarbons such as hydrofluorocarbons.

The building material of the present invention is used for the purpose of improving the appearance, abrasion resistance, weather resistance, scratch resistance, etc. of the surface of the molded product, if necessary, by printing, painting, decorating grain, etc. It can be performed. The building material of the present invention originally has excellent printability and paintability as compared with a resin composed of only an olefin-based monomer, but it is possible to perform surface treatment for the purpose of further improving printability, paintability and the like. . The surface treatment method is not particularly limited, and a physical method, a chemical method or the like can be used, and examples thereof include corona discharge treatment, ozone treatment, plasma treatment, flame treatment, and acid / alkali treatment. it can. Among these, corona discharge treatment is preferable from the viewpoints of ease of implementation, cost, continuous treatment, and the like.

When the building material of the present invention has a planar structure such as a film, a sheet, a tile, a board, etc., such as a flooring material, a wall material, a ceiling material, etc., it can have either a single-layer structure or a multi-layer structure. . Other shapes may have a multi-layered structure if necessary. In the case of a multilayer structure, the composition, composition distribution,
Molecular weight, hydrogenated copolymer of the present invention having different molecular weight distribution,
The composition of the present invention having different kinds of fillers and flame retardants, and different contents, other resin components, materials and the like can be used in each layer. By laminating a plurality of copolymers different from each other, vibration damping performance in a wide temperature range can be exhibited.

There are no particular restrictions on the form of use of the building material of the present invention, but for flooring materials, wall materials, and ceiling materials, structural materials such as concrete, metal, and wood are used as coating materials for the outermost layer. It is also possible to use. Among the building materials of the present invention, flooring materials, wall materials, ceiling materials are provided in the form of sheets, films, tiles, boards, etc., and structural materials such as adhesives, adhesive materials, nails, screws, etc. It is joined to the material. Further, among the building materials of the present invention, the sealing material is provided as, for example, a gasket or the like for improving hermeticity. Specific applications include general housing, office buildings, commercial facilities, public facilities, etc.
Examples include floor materials such as tiles, inner wall materials, ceiling inner wall materials, window frame gaskets, and the like. Especially when it is used as a floor material, an inner wall material, or a ceiling material, it is also excellent in vibration damping and soundproofing.

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. In the following examples, the structure and physical properties of polymers were measured as follows. 1) Styrene content It was measured using an ultraviolet spectrophotometer (manufactured by Shimadzu Corporation, UV-2450) using the copolymer before hydrogenation. 2) Block content of styrene Using a copolymer before hydrogenation, I.M.Kolthoff, et al., J. Pol
ym .Sci. 1,429 (1946). 3) Vinyl bond content It was measured using an infrared spectrophotometer (FT / IR-230, manufactured by JASCO Corporation) using the copolymer before hydrogenation. In the case of a copolymer, it was calculated by the Hampton method, and in the case of a homopolymer, it was calculated by the Morello method.

4) Hydrogenation rate nuclear magnetic resonance apparatus (BRPXER, DPX-400)
Was measured using. 5) Molecular weight and molecular weight distribution GPC [apparatus manufactured by Waters] was used for measurement. Tetrahydrofuran was used as a solvent, and the measurement conditions were a temperature of 35 ° C. The molecular weight is a weight average molecular weight obtained by using a calibration curve (prepared by using the peak molecular weight of standard polystyrene) obtained by measuring the standard polystyrene of the chromatogram. The molecular weight when there are a plurality of peaks in the chromatogram means the average molecular weight obtained from the molecular weight of each peak and the composition ratio of each peak (obtained from the area ratio of each peak in the chromatogram). The molecular weight distribution is the ratio of the obtained weight average molecular weight and number average molecular weight.

6) Crystallization peak and crystallization peak calorific value The crystallization peak and crystallization peak calorific value of the hydrogenated copolymer are D
It was measured by SC (manufactured by Mac Science Co., Ltd., DSC3200S). The temperature was raised from room temperature to 150 ° C. at a temperature rising rate of 30 ° C./min, then the temperature was lowered to −100 ° C. at a temperature lowering rate of 10 ° C./min, and the crystallization curve was measured to confirm the presence or absence of a crystallization peak. When there is a crystallization peak, the temperature at which the peak appears is taken as the crystallization peak temperature, and the crystallization peak calorie is measured. 7) Hardness 1 according to durometer type A according to JIS K6253
The value after 0 seconds was measured. 8) Tensile stress (100-300% stress (Kg / cm ² )), tensile strength (tensile strength (Kg / cm ² )), elongation at break (%) According to JIS K6251, No. 3 dumbbell, crosshead speed 500mm It was measured in minutes.

9) Dunlop impact resilience (%) Measured at 23 ° C. according to BS903. 10) Anti-scratch dynamic vibration type friction tester (AB-3, manufactured by Tester Sangyo Co., Ltd.)
01 type), the surface of the molded sheet (glossy mirror surface) was rubbed 100 times with a friction cloth Kanakin No. 3 cotton and a load of 500 g, and the change in glossiness before and after rubbing was measured with a gloss meter. It was judged. ⊚: Change in glossiness is within 0 to −5 ○: Change in glossiness exceeds −5 to −10 Δ: Change in glossiness exceeds −10 to −50 ×: Change in gloss exceeds −50

11) Abrasion resistance dynamic vibration type friction tester (AB-3, manufactured by Tester Sangyo Co., Ltd.)
01 type), the surface of the molded sheet (textured surface),
Friction cloth Kanakin No. 3 cotton was rubbed with a load of 500 g, and the volume reduction amount after rubbing was used to make a judgment according to the following criteria. ⊚: Volume reduction amount is 0.0 after 10,000 times of rubbing
1 ml or less ○: Volume reduction amount is 0.0 after rubbing 10,000 times
More than 1 and less than or equal to 0.05 ml; volume reduction is 0.0 after 10,000 times of rubbing
5 or less 0.10 ml or less x; volume reduction amount is 0.1 after 10,000 times of rubbing
More than ml

12) Flame resistance A flammability test according to UL94 was conducted, and ranking was carried out based on UL94 criteria. 13) Heat Deformability A heat deformation test (120 ° C) according to JIS K6723
Deformation rate (%) and 150 ° C. deformation rate (%) were measured. The smaller the deformation rate (%), the better the heat resistance. 14) Compression set A compression set test according to JIS K6262 was performed. The measurement conditions are temperature 70 ℃ 22
It's time. 15) Flex resistance A crack initiation test was performed in accordance with JIS K6260.
A dent having a radius of 2.38 mm was put in a strip piece having a length of 150 mm × a width of 25 mm and a thickness of 6.3 mm, and the crack length (mm) after bending 100,000 times was measured. Measurement temperature is 23 ℃
Is.

The components blended are as follows. <Component (1) -1> The hydrogenated copolymer was prepared by the following method. The hydrogenation catalyst used in the hydrogenation reaction in the following examples was prepared by the following method. A reaction vessel purged with nitrogen was charged with 1 liter of dried and purified cyclohexane, 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride was added, and an n-hexane solution containing 200 mmol of trimethylaluminum was added with sufficient stirring. Then, the mixture was reacted at room temperature for about 3 days.

Continuous polymerization was carried out using two stirrers having an internal volume of 10 L and two tank reactors with jackets. From the bottom of the first reactor, a cyclohexane solution having a butadiene concentration of 24% by weight was fed at a feed rate of 4.51 L / hr,
A cyclohexane solution having a styrene concentration of 24% by weight was added to 5.
At a feed rate of 97 L / hr and at a feed rate of 2.0 L / hr, a cyclohexane solution prepared by adjusting the concentration of n-butyllithium to 0.077 g per 100 g of the monomer was further added to N, N, N ′. , N'-Tetramethylethylenediamine in cyclohexane was supplied at a supply rate of 0.44 mol per mol of n-butyllithium, and continuously polymerized at 90 ° C. The reaction temperature is adjusted by the jacket temperature, and the temperature near the bottom of the reactor is about 8
The temperature in the vicinity of the upper portion of the reactor was 8 ° C, and the temperature was about 90 ° C. The average residence time in the polymerization reactor was about 45 minutes, the conversion of butadiene was almost 100%, and the conversion of styrene was 99%. The polymer solution discharged from the first unit was supplied from the bottom of the second unit, and at the same time, a cyclohexane solution having a styrene concentration of 24% by weight was supplied to the bottom of the second unit at a supply rate of 2.38 L / hr, and the temperature was 90 ° C. Was continuously polymerized. The conversion rate of styrene at the outlet of the second unit was 98%.

Next, the hydrogenation catalyst was added to the polymer obtained by continuous polymerization in an amount of 1 as Ti per 100 parts by weight of the polymer.
A hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. The obtained hydrogenated copolymer has a molecular weight of 2
0,000, molecular weight distribution 1.9, styrene content 67
% By weight, block content of styrene 20% by weight, vinyl bond content of butadiene part 14% by weight, hydrogenation rate 99%
Met. From the analysis values of the styrene content and the block content of styrene, the block ratio of styrene is 30%.
As a result of DSC measurement, there was no crystallization peak.

<Component (1) -2> The supply amount of the styrene solution supplied to the first unit was changed to 2.06 L / hr, and the supply amount of the styrene solution supplied to the second unit was 1.37 L / hr. Continuous polymerization was carried out in the same manner as in the component (1) -1 except that it was changed, and then the hydrogenation reaction was carried out in the same manner as in the component (1) -1. The obtained hydrogenated polymer was analyzed and found to have a molecular weight of 20.
The content was 2,000, the molecular weight distribution was 1.9, the styrene content was 45% by weight, the styrene block content was 18% by weight, the vinyl bond content in the butadiene part was 15% by weight, and the hydrogenation rate was 98%. From the analysis values of the styrene content and the block content of styrene, the block ratio of styrene is 33%.

<Component (1) -3> A cyclohexane solution containing 6.5 parts by weight of styrene (concentration: 24% by weight) was prepared by using the same reactor as that used in preparing the component (1) -1. Was thrown in. Next, n-butyllithium and tetramethylethylenediamine were added and polymerized at 50 ° C. for 1 hour, then a cyclohexane solution (concentration 24% by weight) containing 87 parts by weight of butadiene was added and polymerized at 50 ° C. for 1 hour, and styrene was further added. A cyclohexane solution (concentration: 24% by weight) containing 6.5 parts by weight was added and polymerization was carried out at 50 ° C. for 1 hour.
Next, the obtained polymer was hydrogenated in the same manner.
The obtained hydrogenated copolymer had a molecular weight of 210,000, a molecular weight distribution of 1.1, a styrene content of 13% by weight, a styrene block content of 13% by weight, a vinyl bond content of the butadiene part of 73% by weight, and a hydrogenation rate. It was 99%. From the analysis values of the styrene content and the block content of styrene, the block ratio of styrene is 100%.

<Component (1) -4> Using the same reactor as that used for preparing the component (1) -1, a cyclohexane solution having a butadiene concentration of 24% by weight, cyclohexane of n-butyllithium Solution and N, N, N ', N'
-Tetramethylethylenediamine in cyclohexane was continuously fed to the reactor to carry out continuous polymerization. The reaction temperature was adjusted by the jacket temperature, and the temperature near the top of the reactor was about 90 ° C. The average residence time in the polymerization reactor was about 45 minutes, and the conversion of butadiene was almost 100%. Next, the polymer obtained by continuous polymerization was subjected to hydrogenation reaction in the same manner. The obtained hydrogenated polymer had a molecular weight of 180,000, a molecular weight distribution of 1.9, a styrene content of 0% by weight, and a vinyl bond content of a butadiene portion of 22.
% By weight.

<Component (1) -5> Polyvinyl chloride elastomer, Sumiflex K580
CF1 (Sumitomo Bakelite). <Component (2) -1> Polypropylene resin <Homo PP>, PM801A (manufactured by Sun Allomer) MFR (230 ° C, 2.16 kg); 13 g / min. <Component (2) -2> As the polyphenylene ether resin, poly (2,6-dimethyl-1,4-phenylene) ether and reduced viscosity: 0.54 were used. <Component (2) -3> Polypropylene resin <Random PP
>, PC630A (manufactured by Sun Allomer) MFR (230
C, 2.16 kg); 7.5 g / min.

<Component (2) -4> Hydrogenated product of styrene / butadiene block copolymer,
Tuftec H1221 (manufactured by Asahi Kasei) <Component (2) -5> Polystyrene resin <HIPS>, 475D (manufactured by A & M styrene) <Component (3) -1> Magnesium hydroxide, Kisuma 5A (manufactured by Kyowa Chemical Industry) <Component (3 ) -2> Triphenyl phosphate (manufactured by Daihachi Chemical Industry) <Component (4) -1> Organic peroxide, Perhexin 25B (manufactured by NOF Corporation) <Component (4) -2> Organic peroxide, Perhexa 25B (Made by Nippon Oil & Fat)

Example 1 Using component (1) -1 as a hydrogenated copolymer, rolling was carried out with a 3.5 inch roll at 200 ° C., and thereafter a hydraulic press was pressed at 200 ° C. and 100 kg / cm ² . Molding was performed to form a molded sheet having a thickness of 2 mm. The physical properties are shown in Table 1. Comparative Examples 1 and 7 Using the component (1) -2 as the hydrogenated copolymer and the component (1) -5 as the polyvinyl chloride elastomer, a 2 mm thick molded sheet was prepared in the same manner as in Example 1. The physical properties are shown in Table 1. Examples 2 to 6 Component (1) -1 was used as the hydrogenated copolymer, and after mixing the components shown in Table 1 with a Henschel mixer, 230 ° C was obtained with a twin-screw extruder having a diameter of 30 mm (Example 2, 4-6) and 270
Melt kneading was carried out under the condition of ° C (Example 3) to obtain pellets of the composition. Using this composition, in the same manner as in Example 1,
A 2 mm thick molded sheet was prepared. The physical properties are shown in Table 1.

Furthermore, the dynamic viscoelastic spectrum of the composition of Example 5 was analyzed by ARES dynamic analyzer (ARES-2KF).
RTN1-FCO-STD; Rheometric Scientific F.E.) is used, and torsion mode (measurement frequency:
1 Hz). The dynamic viscoelastic spectrum is shown in FIG. The tan δ peak is near room temperature, which means that the vibration damping property is good. Further, in Example 6, strips (127 mm × 12.7 mm) were cut out from the molded sheet, and a flammability test according to UL94 was also performed. V-0
It has a rank and can be advantageously used for building materials that require flame retardancy.

Comparative Examples 2 to 6 Component (1) -2, Component (1) -3 as hydrogenated copolymer,
Component (1) -4 was used, and the components shown in Table 1 were mixed with a Henschel mixer and then mixed with a twin-screw extruder having a diameter of 30 mm.
Melt kneading was carried out under the condition of 0 ° C. to obtain pellets of the composition. Using this composition, a 2 mm thick molded sheet was prepared in the same manner as in Example 1. The physical properties are shown in Table 1. From these results, it was found that the building material of the present invention has excellent vibration damping properties, and also has excellent strength, scratch resistance, and abrasion resistance. It was also found that even when a filler was added, it did not bleed and maintained its transparency and physical properties. Furthermore, it has been found that it behaves almost the same as the tensile stress of a polyvinyl chloride elastomer of the same hardness, has a feeling very close to that of a polyvinyl chloride elastomer, and is effective as a substitute for it.

[0060]

[Table 1]

Examples 7 to 9 Component (1) -1 was used as the hydrogenated copolymer, and after mixing the components shown in Table 2 with a Henschel mixer, the conditions were 230 ° C. in a twin-screw extruder having a diameter of 30 mm. And melt-kneaded to obtain pellets of the composition. Using this composition, a 2 mm thick molded sheet was prepared in the same manner as in Example 1. The physical properties are shown in Table 2.

[0062]

[Table 2]

Example 10 50% by weight of component (1) -1 as a hydrogenated copolymer, 40% by weight of PPE of component (2) -2, and 10% by weight of triphenyl phosphate of component (3) -2. Was mixed with a Henschel mixer, and then melt-kneaded under a condition of 270 ° C. with a twin-screw extruder having a diameter of 30 mm to obtain pellets of the composition. When a flammability test was conducted using this composition, it was V-0 rank. Example 11 A composition was prepared in the same manner as in Example 10, except that the component (1) -1 was 40 parts by weight and 10 parts by weight of the HIPS of the component (2) -5 was mixed therein. When a flammability test was conducted in the same manner as in Example 10, it was V-0 rank.

Examples 12 and 13 Using the organic peroxide of component 4 as a crosslinking agent, the hydrogenated copolymer was dynamically crosslinked to produce a crosslinked hydrogenated copolymer. The hydrogenated copolymer and the organic peroxide were mixed at the ratio shown in Table 3, and then melt-kneaded with a twin-screw extruder to obtain pellets of a crosslinked hydrogenated copolymer. The kneading temperature is 220 ° C. in Example 12, and Example 1
In the case of 3, the temperature was 210 ° C. The crosslinked hydrogenated copolymer was compression molded to prepare a 2 mm thick molding sheet, which was used as a test piece. In addition, a 6.3 mm-thick sheet was separately prepared and used as a test piece for a bending resistance test. The physical properties of the test pieces were measured, and the results are shown in Table-3.

[0065]

[Table 3]

[0066]

EFFECTS OF THE INVENTION According to the present invention, the strength, abrasion resistance, scratch resistance, vibration damping, etc. are excellent, and the elastic modulus, feel, etc. peculiar to polyvinyl chloride resin are exhibited, and the filler is used at a higher concentration. Alternatively, it is possible to provide a building material, particularly a flooring material, a wall material, a ceiling material, or a sealing material composition, which can maintain transparency and the above-mentioned physical properties even if it contains a flame retardant.

[Brief description of drawings]

1 is a diagram showing a dynamic viscoelastic spectrum of the composition of Example 5. FIG.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 3/00 C08K 3/00 4J002 5/521 5/521 4J026 C08L 21/00 C08L 21/00 4J100 25 / 10 25/10 53/02 53/02 101/00 101/00 E04B 1/684 E04B 1/92 1/92 E04F 13/18 A E04F 13/18 15/10 104A 15/10 104 E04B 1/68 D ( 72) Inventor Masahiro Sasakawa 1-3-1 Yokou, Kawasaki-ku, Kanagawa Prefecture Asahi Kasei Corporation F-term (reference) 2E001 DA01 DG01 DH31 DH37 DH39 FA10 HD11 HE01 MA01 MA04 2E110 AA02 AA26 AA33 AA48 AA64 AB03 AB04 AB05 AB23 BA23 BA23 BA12 DA12 DC15 DC21 DD20 GA17W GA28W GA29W GA32W GA33W GA34W GB42W GB55W 2E220 AA02 AA16 AA19 AA25 AB12 AB14 AB24 AC01 BA01 BA19 DA02 DA19 DB05 DB09 EA01 FA01 GA02X GA22X GA24X GA25X GA2 6X GB32X GB34X GB39X 4F071 AA01 AA10 AA12X AA22X AA75 AA76 AA78 AA84 AE07 AE17 AH03 BC01 BC03 4F074 AHA32B HA01 HA01 HA06B02B01B06B02BA01B024A07A02 4J100 AB02P AS00Q CA04 CA31 DA01 DA24 HA03 HG03 JA67

Claims (10)

[Claims] 1. A hydrogenated copolymer obtained by adding hydrogen to a copolymer composed of a conjugated diene and a vinyl aromatic compound, wherein (a) the vinyl aromatic compound in the hydrogenated copolymer. The content is more than 50% by weight and 90% by weight or less, (b) the block (H) content of the vinyl aromatic compound in the hydrogenated copolymer is 40% by weight or less, and (c) the hydrogenated copolymer. Weight average molecular weight of 50,000-100
(D) A building material comprising a hydrogenated copolymer in which 75% or more of double bonds based on the conjugated diene compound in the hydrogenated copolymer are hydrogenated. 2. The hydrogenated copolymer according to claim 1, 5 parts by weight to
A building material comprising a composition composed of 95 parts by weight and 5 parts by weight to 95 parts by weight of a thermoplastic resin and / or a rubber-like polymer. 3. 5 parts by weight of the hydrogenated copolymer according to claim 1.
95 parts by weight and 5 parts by weight to 9 parts by weight of filler and / or flame retardant
A building material consisting of a composition of 5 parts by weight. 4. A component comprising (1) 5% by weight to 95% by weight of the hydrogenated copolymer according to claim 1 and (2) 5% by weight to 95% by weight of a thermoplastic resin and / or a rubbery polymer. 1) +
With respect to the total amount of the component (2) of 5 to 95 parts by weight,
(3) A building material comprising a composition composed of 5 parts by weight to 95 parts by weight of a filler and / or flame retardant component. 5. The hydrogenated copolymer has a differential scanning calorimetry (DS).
In C), the crystallization peak is substantially absent in the range of -50 ° C to 100 ° C.
Building material according to any one of. 6. The block (H) content of the vinyl aromatic compound in the hydrogenated copolymer is less than 10% by weight.
The building material according to any one of to 5. 7. The building material according to claim 1, wherein the block (H) content of the vinyl aromatic compound in the hydrogenated copolymer is 10 to 40% by weight. 8. The building material according to claim 1, wherein the hydrogenated copolymer is a hydrogenated product of a copolymer having at least one structure selected from the following general formulas. S S-H S-H-S (S-H) m-X (S-H) n-X- (H) p (where S is a random copolymer block of a conjugated diene and a vinyl aromatic compound) And H is a vinyl aromatic compound polymer block, m is an integer of 2 or more, and n is
And p are integers of 1 or more. X represents a coupling agent residue. ) 9. The building material according to claim 1, wherein the building material is a flooring material, a wall material, a ceiling material or a sealing material. 10. The building material according to claim 1, wherein the building material has a foam structure.