JPWO2001085818A1 - Block copolymer and composition containing said copolymer - Google Patents

Abstract

(57) [Abstract] A hydrogenated block copolymer that, as a polyolefin resin composition, can provide molded articles with an excellent balance of physical properties such as impact resistance and moldability, and that, as an adhesive composition, can provide a composition with an excellent balance of adhesive properties and melt viscosity stability under high-temperature heating. The hydrogenated block copolymer has at least one polymer block primarily composed of a vinyl aromatic hydrocarbon and at least one polymer block primarily composed of a conjugated diene compound, and has a vinyl bond content V (%) based on the conjugated diene compound of 37% or more but less than 70%, wherein: (a) the total hydrogenation rate H (%) of unsaturated double bonds based on the conjugated diene compound satisfies the following relationship: V < H < 1.25 × V + 10 50 ≦ H < 80; and (b) the hydrogenation rate of vinyl bonds is 82% or more.

Description

Detailed Description of the Invention <Technical Field> The present invention relates to a novel hydrogenated block copolymer, in which the hydrogenation rate of a block copolymer of a vinyl aromatic hydrocarbon having a specific vinyl bond content and a conjugated diene compound is controlled within a specific range, and to a block copolymer composition comprising the block copolymer and a polyolefin resin, or the block copolymer composition comprising the block copolymer and a tackifier.

More specifically, the present invention relates to an impact-resistant resin composition having excellent impact resistance, particularly low-temperature impact resistance and moldability; a soft resin composition having excellent flexibility, transparency, and moldability; and a flexible resin composition having excellent flexibility, elasticity, and moldability.

The present invention also relates to an adhesive composition which has an excellent balance of adhesive properties such as adhesive strength and holding power, and which also has excellent melt viscosity stability when heated at high temperatures.

<Background Art> Polyolefin resins generally have excellent chemical resistance and mechanical properties, and are therefore widely used in a wide range of applications, from machine parts and automobile parts to household goods and various containers, etc. However, their impact strength, particularly at low temperatures, is insufficient, which has limited their intended uses.

Therefore, in order to solve this problem, many proposals have been made to add a rubber component to polyolefin. For example, Japanese Patent Publication No. 47-26369 discloses that impact resistance can be improved by adding a styrene-butadiene block copolymer and a thermoplastic elastomer to a polyolefin resin. In addition, Japanese Patent Laid-Open Publication No. 6-172593 discloses a composition comprising a polyolefin resin and a hydrogenated block copolymer. However, these methods use ordinary block copolymers, and therefore the balance between impact resistance, particularly low-temperature impact resistance, and molding processability such as thermal stability and fluidity is insufficient.

Recently, in response to environmental issues, the development of non-halogenated transparent polymeric materials has progressed, and particularly in the field of sheets and films, there is a demand for softer and more transparent polypropylene resins, and attempts have been made to improve them. For example, Japanese Patent Laid-Open Publication No. 6-287365 discloses a composition consisting of polypropylene and a hydrogenated diene copolymer. However, the composition obtained by this method has poor transparency and insufficient processability.

Meanwhile, hot-melt adhesives have become widely used in recent years due to concerns about environmental pollution and working conditions. Vinyl aromatic hydrocarbon-conjugated diene block copolymers (SBS) are widely used as the base polymer for hot-melt adhesives. For example, Japanese Patent Publication No. 56-49958 discloses a pressure-sensitive adhesive composition using such a block copolymer. However, SBS generally has poor thermal stability and an insufficient balance between holding power and tackiness, and improvements in these areas have been desired. As a method for improving these issues, Japanese Patent Laid-Open Publication No. 64-81877 discloses an adhesive composition comprising a triblock copolymer and a diblock copolymer. Furthermore, Japanese Patent Laid-Open Publication No. 63-248817 discloses an adhesive composition comprising a block copolymer obtained by coupling with a specific bifunctional coupling agent (aliphatic monoester, specific dihalogen compound).

In response to such a demand for improvement, Japanese Patent Publication No. 4-68343 (US Pat. No. 4,994
508) and JP-A-10-219040 disclose compositions of a block copolymer obtained by specifically hydrogenating a block copolymer of a vinyl aromatic hydrocarbon and butadiene, and a polyolefin resin. However, these documents do not specifically disclose the hydrogenated block copolymer used in the present invention, and further improvement is desired in terms of the balance between low-temperature impact resistance and molding processability.

Furthermore, Japanese Patent Publication No. 5-69874 (USP 4,994,508) describes a composition of a tackifier and a block copolymer obtained by specifically hydrogenating a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene compound. However, this publication does not specifically disclose the hydrogenated block copolymer used in the present invention, and further improvement is desired in terms of the balance between holding power and tackiness, as well as the melt viscosity stability under high temperature heating.

The object of the present invention is to provide: 1) a polyolefin resin composition having an excellent balance of physical properties such as impact resistance, particularly low-temperature impact resistance, rigidity, molding processability (fluidity), and heat aging resistance (hereinafter referred to as an impact-resistant resin composition); 2) a resin composition having excellent flexibility, transparency, and molding processability (hereinafter referred to as a soft resin composition); 3) a resin composition having excellent flexibility, elasticity, and molding processability (hereinafter referred to as a flexible resin composition); and 4) a pressure-sensitive adhesive composition having an excellent balance of adhesive properties such as adhesive strength and holding power, and excellent melt viscosity stability when heated at high temperatures.

Disclosure of the Invention As a result of extensive research aimed at solving the above-mentioned problems, the present inventors have found that a hydrogenated block copolymer, in which the hydrogenation rate of a block copolymer of a vinyl aromatic hydrocarbon having a specific vinyl bond content and a conjugated diene compound is controlled within a specific range, exhibits excellent effects in modifying polyolefin resins. The inventors then discovered that a composition comprising the hydrogenated block copolymer and a polyolefin resin, or a composition comprising a tackifier, effectively solves the above-mentioned problems, leading to the completion of the present invention. Specifically, the present invention provides: 1. (1) a hydrogenated block copolymer having at least one polymer block mainly composed of a vinyl aromatic hydrocarbon and at least one polymer block mainly composed of a conjugated diene compound, wherein the vinyl bond content V (%) based on the conjugated diene compound is 37% or more but less than 70%, and wherein: (a) a total hydrogenation rate H (
%) satisfies the following relational formula: V<H<1.25×V+10 50≦H<80 (b) a hydrogenated block copolymer having a hydrogenation rate of vinyl bonds of 82% or more; 2. (1) the hydrogenated block copolymer according to 1 above, and (2) a block copolymer composition comprising a polyolefin resin; 3. The composition comprises 1 to 100 parts by weight of the total weight of the components (1) and (2).
50 parts by weight of component (1) and 99 to 50 parts by weight of component (2),
3. The block copolymer composition according to 2 above, wherein the (1) component and the (2) component further satisfy the following requirements: (c) a content of vinyl aromatic hydrocarbon of 5 to 50% by weight, (d) a melt flow rate of 0.5 to 100 g/10 min, and 4. The composition contains 1 to 100 parts by weight of the total weight of the (1) component and the (2) component.
95 parts by weight of component (1) and 99 to 5 parts by weight of component (2),
5. The block copolymer composition according to 2 above, which further satisfies the following requirements: (c) the content of vinyl aromatic hydrocarbon is 5 to 35% by weight, (d) the number average molecular weight is more than 30,000 and less than 330,000, and 6. The composition is characterized in that the content of the vinyl aromatic hydrocarbon is 5 to 35% by weight, and (e) the number average molecular weight is more than 30,000 and less than 330,000, and 7. The composition is characterized in that the content of the vinyl aromatic hydrocarbon is 5 to 35% by weight, and (f) the number average molecular weight is more than 30,000 and less than 330,000,
95 to 95 parts by weight of component (1) and 80 to 5 parts by weight of component (2), further comprising component (1)
(3) 5 to 300 parts by weight of a non-aromatic rubber softener and (
4) The block copolymer composition according to 2 above, which comprises 500 parts by weight or less of an inorganic filler, and component (1) further satisfies the following requirements: (c) the content of vinyl aromatic hydrocarbon is 5 to 50% by weight, (d) the number average molecular weight is 50,000 to 1,000,000, 6. (1) A hydrogenated product of a block copolymer having at least one polymer block mainly composed of vinyl aromatic hydrocarbon and at least one polymer block mainly composed of a conjugated diene compound, and having a vinyl bond content V (%) based on the conjugated diene compound of 30% or more and less than 70%, wherein (a) the total hydrogenation rate H(
%) satisfies the following relationship: V<H<2×V+10 30≦H<80 (b) 100 parts by weight of a hydrogenated block copolymer having a hydrogenation rate of vinyl bonds of 82% or more, and (2) 20 to 400 parts by weight of a tackifier (based on 100 parts by weight of component (1)).
7. The block copolymer composition according to 6 above, wherein component (1) further satisfies the following requirements: (c) the content of vinyl aromatic hydrocarbon is 5 to 60% by weight, (d) the peak molecular weight is 50,000 to 300,000, 8. The component (1) is (1-A) a hydrogenated product of a block copolymer having one polymer block mainly composed of vinyl aromatic hydrocarbon and one polymer block mainly composed of a conjugated diene compound, and having a vinyl bond content V (%) based on the conjugated diene compound of 30% or more and less than 70%, wherein (a) the total hydrogenation rate H(
%) satisfies the following relational expressions: V<H<2×V+10 30≦H<80 (b) a hydrogenation rate of vinyl bonds of 82% or more; (c) a content of vinyl aromatic hydrocarbons of 5 to 60% by weight; (1-B) a hydrogenated block copolymer having at least two polymer blocks mainly composed of vinyl aromatic hydrocarbons and at least one polymer block mainly composed of a conjugated diene compound,
A hydrogenated block copolymer having a vinyl bond content V (%) based on a conjugated diene compound of 30% or more and less than 70%, wherein: (a) a total hydrogenation rate H(
%) satisfies the following relationship: V<H<2×V+10 30≦H<80 (b) a hydrogenation rate of vinyl bonds of 82% or more (c) a content of vinyl aromatic hydrocarbons of 5 to 60% by weight, and 80 to 10% by weight of a hydrogenated block copolymer, wherein the average molecular weights of components (1-A) and (1-B) are 50,000 to 300,000.

<Best Mode for Carrying Out the Invention> The present invention is described in detail below.

The hydrogenated block copolymer of component (1) used in the present invention is a hydrogenated product of a block copolymer having at least one polymer block mainly composed of a vinyl aromatic hydrocarbon and at least one polymer block mainly composed of a conjugated diene compound. The vinyl aromatic monomer units include alkylstyrenes such as styrene, α-methylstyrene, p-methylstyrene, and p-tert-butylstyrene;
One or more of the conjugated diene compounds are selected from the group consisting of paramethoxystyrene, vinylnaphthalene, etc., and styrene is particularly preferred. The conjugated diene compounds are diolefins having a pair of conjugated double bonds, such as 1,3-butadiene, 2-methyl-1,3-
Butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-
Examples of the alkylene include pentadiene and 1,3-hexadiene, and particularly common examples include 1,3-butadiene and isoprene. These may be used singly or in combination of two or more.

As a method for producing a block copolymer before hydrogenation, for example, the method described in Japanese Patent Publication No. 1961-1962 is described.
Publication No. 286, Japanese Patent Publication No. 17979-1979, Publication No. 32415-1977
, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. 2423-1973, Japanese Patent Publication No. 48-2423
4106 Publication, Special Publication No. 56-28925, Special Publication No. 51-49567
JP-A-59-166518, JP-A-60-186577, etc.
By these methods, block copolymers having the general formula (A-B)_n, A-(B-A)_n, B-(A-B)_n (In the above formula, A is a polymer block mainly composed of vinyl aromatic hydrocarbons,
B is a polymer mainly composed of a conjugated diene compound.
The boundaries do not necessarily have to be clearly distinguished. Also, n is 1 or more, generally an integer between 1 and 5.
) Or the general formula [(B-A)_n］_m+1-X, [(A-B)_n］_m+1-X [(B-A)_n-B]_m+1-X, [(A-B)_n-A]_m+1-X (In the above formula, A, B, and n are the same as above, and X is, for example, silicon tetrachloride, tetrachlorosilane,
Tin chloride, epoxidized soybean oil, di- to hexa-functional epoxy group-containing compound, polyhalogen
Polyvinyl compounds such as fluorinated hydrocarbons, carboxylic acid esters, and divinylbenzene
The residue of any coupling agent or initiator, such as a polyfunctional organolithium compound, is shown.
m is an integer of 1 or more, generally 1 to 10.
The polymer structures may be the same or different.
In the above, the polymer block mainly composed of vinyl aromatic hydrocarbon is
The block is a compound containing 50% by weight or more, preferably 70% by weight or more, of vinyl aromatic hydrocarbons.
A copolymer block of a vinyl aromatic hydrocarbon and a conjugated diene compound and/or
or vinyl aromatic hydrocarbon homopolymer block, mainly composed of conjugated diene compounds
The polymer block is preferably a polymer block containing a conjugated diene compound in an amount of more than 50% by weight.
Copolymer of a conjugated diene compound containing 70% by weight or more of a vinyl aromatic hydrocarbon
Copolymer block and/or conjugated diene compound homopolymer block.
The vinyl aromatic hydrocarbons in the block may be uniformly distributed or tapered.
In addition, the vinyl aromatic hydrocarbon may be uniformly distributed in the copolymer portion.
There are multiple areas that are distributed in a tapered shape and/or areas that are distributed in a tapered shape.
The hydrogenated block copolymer used in the present invention may be
The block copolymer represented by the above general formula is preferably water-soluble within a range that satisfies the above requirements.
It may be any mixture of additives.

In the present invention, the vinyl bond content V (%) based on the conjugated diene compound in the block copolymer before hydrogenation is 37% or more and less than 70%, preferably 40% or more,
The vinyl bond content is preferably less than 65%, more preferably 47% or more and less than 63%. The vinyl bond content here refers to the proportion of 1,2-bonds and 3,4-bonds among the conjugated diene compounds incorporated in the block copolymer in the bonding modes of 1,2-bonds, 3,4-bonds and 1,4-bonds.
This is the proportion of those incorporated via 4-bonds. If the vinyl bond content is outside the range specified in the present invention, the desired performance cannot be obtained. For example, in the above-mentioned impact-resistant resin composition, if the vinyl bond content is less than 37% by weight, the affinity between the hydrogenated block copolymer and the polyolefin resin is insufficient, resulting in a deterioration of the essential low-temperature impact resistance and a decrease in processability. On the other hand, if it is 70% by weight or more, the affinity with the polyolefin resin becomes excessive, resulting in a resin composition with low low-temperature impact resistance and low rigidity. Furthermore, in the flexible resin composition, if the vinyl bond content is less than 37% by weight, the affinity between the hydrogenated block copolymer and the polyolefin resin is insufficient, resulting in a deterioration of transparency and flexibility, and a decrease in processability. On the other hand, even if it is 70% by weight or more, the resin composition will have low transparency.

In the adhesive composition, the vinyl bond content V (%) based on the conjugated diene compound in the block copolymer before hydrogenation is 30% or more and less than 70%, preferably 35% or more and less than 68%, and more preferably 40% or more and less than 65%.
If the content exceeds this range, the affinity with the tackifier will be insufficient, resulting in poor adhesion and compatibility.

The vinyl bond amount can be adjusted during production of the block copolymer using, as a vinyl amount adjuster, an ether compound such as dimethyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, or diethylene glycol dibutyl ether, or a tertiary amine such as trimethylamine, triethylamine, N,N,N',N'-tetramethylethylenediamine, or diazobicyclo[2,2,2]octane.

The hydrogenated block copolymer used in the present invention can be obtained by hydrogenating the above-mentioned block copolymer (hydrogenation reaction). Catalysts used in the hydrogenation reaction include: (1) supported heterogeneous catalysts in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, etc.; (2) so-called Ziegler catalysts in which transition metal salts such as organic acid salts or acetylacetonates of Ni, Co, Fe, and Cr are used with reducing agents such as organic aluminum; and (3) Ti, Ru, Rh, Zr
Specific methods for hydrogenation reaction are disclosed in Japanese Patent Publication Nos. 42-8704 and 43-6706.
In this method, hydrogenation is carried out in a hydrocarbon solvent in the presence of a hydrogenation catalyst to obtain a hydrogenated product. In this case, the hydrogenation rate of the block copolymer can be controlled by a variety of factors, including the reaction temperature, reaction time,
This can be controlled by adjusting the amount of hydrogen supplied, the amount of catalyst, etc.

The hydrogenated block copolymer used in the present invention must have a total hydrogenation rate H (%) of unsaturated double bonds based on the conjugated diene compound that satisfies the following relationship: V<H<1.25×V+10 50≦H<80, preferably V<H<1.25×V+10 55≦H<78, and more preferably V+5<H<1.25×V+10 55≦H<78.

In a composition with a polyolefin resin, if the total hydrogenation rate H is less than the vinyl bond amount V before hydrogenation, the heat aging resistance of the resin composition is poor. Furthermore, in an impact-resistant resin composition, the balance between low-temperature impact resistance and rigidity is deteriorated, and in a soft resin composition, transparency is deteriorated. On the other hand, if the total hydrogenation rate H is 1.25 x V + 10 or more, the processability of the resin composition is reduced. Furthermore, if the total hydrogenation rate H is less than V + 5, the processability of the resin composition is deteriorated.
Even when H<1.25×V+10 is satisfied, if H is 80% or more, the processability is reduced compared to the resin composition within the range of the present invention.

Furthermore, the hydrogenated block copolymer used in the adhesive composition of the present invention needs to have a total hydrogenation rate H (%) of unsaturated double bonds based on the conjugated diene compound satisfying the following relational expressions: V<H<2×V+10 30≦H<80, preferably V<H<2×V+10 35≦H<78, and more preferably V<H<2×V+5 35≦H<78.

In the adhesive composition, when the total hydrogenation rate H is equal to or less than the vinyl bond amount V before hydrogenation or equal to or more than 2×V+10, the balance between holding power and adhesiveness is poor, which is not preferable.
Even when the above condition is satisfied, if the content is 80% or more, the adhesiveness will be reduced compared to the adhesive composition falling within the range of the present invention.

In the present invention, the hydrogenation rate of vinyl bonds in the conjugated diene before hydrogenation in the hydrogenated block copolymer must be 82% or more, preferably 85% or more, and more preferably 90% or more. If the hydrogenation rate of vinyl bonds is less than 82%, the thermal stability and melt viscosity stability under high temperature heating will be poor, which is undesirable.
Here, the hydrogenation rate of vinyl bonds refers to the proportion of hydrogenated vinyl bonds among the vinyl bonds in the conjugated diene incorporated in the block copolymer before hydrogenation.

Although there are no particular limitations on the hydrogenation rate of aromatic double bonds based on vinyl aromatic hydrocarbons in the block copolymer, it is preferable that the hydrogenation rate is 50% or less, preferably 30% or less, and more preferably 20% or less. The hydrogenation rate can be determined by an infrared spectrophotometer, a nuclear magnetic resonance (NMR) spectrometer, or the like.

The vinyl aromatic hydrocarbon content of the hydrogenated block copolymer used in the present invention is preferably 5 to 50% by weight, more preferably 8 to 45% by weight, and most preferably 10 to 40% by weight. If the vinyl aromatic hydrocarbon content of the hydrogenated block copolymer is outside this range, the properties desired by the present invention will not be obtained.

In a composition with a polyolefin resin, for example, when used in an impact-resistant resin composition, the content of vinyl aromatic hydrocarbon in the hydrogenated block copolymer is 5% by weight.
If the content is less than 50% by weight, the rigidity may be poor, and if it exceeds 50% by weight, the low-temperature impact resistance may be poor. In the present invention, it is recommended that the vinyl aromatic hydrocarbon content of the hydrogenated block copolymer suitable for the flexible resin composition is 5 to 35% by weight, preferably more than 8% by weight and less than 30% by weight, and more preferably more than 10% by weight and less than 25% by weight. If the content of vinyl aromatic hydrocarbon is 5% by weight or less, the blocking resistance of the film molded from the flexible resin composition will deteriorate, and if it exceeds 35% by weight, the blocking resistance of the film will deteriorate.
If the temperature is above this, the flexibility and transparency of the flexible resin composition will be poor.

In addition, in the adhesive composition, if the content of vinyl aromatic hydrocarbon in the hydrogenated block copolymer is less than 5% by weight, the holding power may be poor, and if it exceeds 60% by weight, the adhesiveness may be poor.

In a composition with a polyolefin resin, for example, when used in an impact-resistant resin composition, the melt flow rate of the hydrogenated block copolymer (JIS K6758
(based on the standard: 230°C, 2.16 kg load) is preferably 0.5 to 100 g/10
The melt flow rate is preferably 1 to 80 g/10 min, more preferably 1 to 80 g/10 min, and most preferably 2 to 50 g/10 min. If the melt flow rate is less than 0.5 g/10 min, the moldability of the resulting composition will be poor, and if it exceeds 100 g/10 min, the low-temperature impact resistance may be reduced. It is recommended that the number average molecular weight of a suitable hydrogenated block copolymer is more than 30,000 and less than 330,000, preferably more than 50,000 and less than 250,000, and more preferably more than 70,000 and less than 200,000. In particular, the number average molecular weight of a hydrogenated block copolymer suitable for a soft resin composition is more than 30,000 and less than 330,000, preferably more than 50,000 to 250,000.
It is preferably less than 250,000, more preferably more than 70,000 and less than 200,000. Within this range, the flexible resin composition has a good balance between moldability and flexibility.

Furthermore, in the present invention, it is recommended that the hydrogenated block copolymer suitable for the flexible resin composition has a number-average molecular weight of 50,000 to 1,000,000, preferably 70,000 to 500,000, and more preferably 90,000 or more and less than 330,000. If the number-average molecular weight is less than 50,000, the strength of the flexible resin composition will decrease, and if it exceeds 1,000,000, the moldability will be poor.

On the other hand, in the present invention, the molecular weight of the hydrogenated block copolymer suitable for the adhesive composition has a peak molecular weight of 50,000 to 300,000, preferably 60,000 to 250,000, and more preferably 70,000 to 200,000, calculated in terms of standard polystyrene, as measured by GPC.
If the peak molecular weight of the adhesive composition is less than 50,000, the holding power of the adhesive composition is poor, and if it exceeds 300,000, the melt viscosity increases, and the coating performance of the adhesive composition is poor, which is undesirable.

In the adhesive composition of the present invention, the hydrogenated block copolymer of component (1) is a copolymer of (1-A) a vinyl aromatic hydrocarbon copolymer and a conjugated diene compound copolymer, and the copolymer of (1-B) a vinyl aromatic hydrocarbon copolymer and a conjugated diene compound copolymer, and the copolymer of (1-C) a vinyl aromatic hydrocarbon copolymer and a conjugated diene compound copolymer, and the copolymer of (1-B ...
20 to 90% by weight, preferably 25 to 80% by weight, of a hydrogenated block copolymer in which the total hydrogenation rate H, the hydrogenation rate of vinyl bonds, and the content of vinyl aromatic hydrocarbon satisfy the above requirements. (1-B) A hydrogenated block copolymer having at least two polymer blocks mainly composed of vinyl aromatic hydrocarbons and at least one polymer block mainly composed of a conjugated diene compound,
Furthermore, the hydrogenated block copolymer 80 satisfies the above requirements in terms of the vinyl bond amount V, the total hydrogenation rate H, the hydrogenation rate of vinyl bonds, and the content of vinyl aromatic hydrocarbons.
It is recommended to use a hydrogenated block copolymer comprising from 10 to 10% by weight, preferably from 75 to 20% by weight, in order to obtain an adhesive composition having an excellent balance of holding power, tackiness and melt viscosity.

[0030] In terms of the balance between holding power and adhesiveness and the melt viscosity of the adhesive composition, it is particularly preferred that the molecular weights of these hydrogenated block copolymers (peak molecular weights converted into standard polystyrene when measured by GPC) for component (1-A) be 30,000 to 150,000, preferably 40,000 to 140,000, and more preferably 50,000 to 130,000, and that for component (1-B) be 100,000 to 300,000, preferably 120,000 to 280,000, and more preferably 140,000 to 260,000. The average molecular weights of component (1-A) and component (1-B) need to be set within the molecular weight range explained above for the molecular weight of the hydrogenated block copolymer of component (1).

In the present invention, the hydrogenated block copolymer consisting of components (1-A) and (1-B) can be obtained by, for example, polymerizing styrene in an inert hydrocarbon solvent using an organolithium compound as a polymerization initiator, then polymerizing butadiene, and optionally repeating these steps to obtain two types of styrene-butadiene block copolymers with different molecular weights, which are then polymerized separately and mixed. The molecular weight can be adjusted by controlling the amount of organolithium compound. Composition (A) can be prepared by blending the polymerization solutions of the components in a predetermined composition after the polymerization reaction, in which active species are deactivated by adding water, alcohol, acid, etc., followed by separating the polymerization solvent by, for example, steam stripping, and then drying. Alternatively, the polymers obtained by separating and drying the polymerization solvents individually can be blended using a roll or the like.

Furthermore, a hydrogenated block copolymer consisting of component (1-A) and component (1-B) can also be obtained by a method other than that described above. That is, after polymerizing component (1-A) in the same manner as above, a suitable coupling agent is added to the polymerization system in a predetermined amount relative to the organolithium compound to obtain a copolymer product, component (1-B), and the desired composition is obtained in the same reaction system. When this method is used, the peak molecular weight of component (1-B) is an integer multiple of the peak molecular weight of component (1-A),
Although the monoalkenyl aromatic compound content of component (1-A) and component (1-B) is the same and the structure is limited, this method is industrially advantageous compared to the above-mentioned method.

As the coupling agent, a bifunctional coupling agent is preferably used.
Examples of such compounds include halogenated silicon compounds such as dichlorodimethylsilane and phenylmethyldichlorosilane, alkoxy silicon compounds such as dimethyldimethoxysilane, tin compounds such as dichlorodimethyltin, ester compounds such as methyl benzoate, vinyl arenes such as divinylbenzene, and difunctional epoxy compounds.

In the block copolymer composition of the present invention, two or more hydrogenated block copolymers of component (1) may be used, each having a different vinyl content V before hydrogenation, a different total hydrogenation rate H, a different melt flow, a different vinyl aromatic hydrocarbon content, or a different polymer structure. By using two or more hydrogenated block copolymers satisfying the requirements of the present invention, the balance of various physical properties can be further improved. Furthermore, the hydrogenated block copolymer used in the present invention may be a modified polymer in which a polar group-containing functional group selected from nitrogen, oxygen, silicon, phosphorus, sulfur, and tin is bonded to the polymer, or a polymer modified by an addition reaction with an unsaturated carboxylic acid or its derivative to contain the functional group.

The hydrogenated block copolymer of the present invention can be obtained by removing the solvent from the solution of the hydrogenated block copolymer obtained as described above using a conventional method. If necessary, a reaction terminator, antioxidant, neutralizing agent, surfactant, etc. may also be used in the deashing step of metal salts.

The polyolefin resin of component (2) used in the present invention may be ethylene,
There are no particular limitations on the resin as long as it is obtained by polymerizing one or more monomers selected from α-olefins having 3 to 12 carbon atoms, such as propylene, 1-butene, isobutylene, 4-methyl-1-pentene, and 1-octene. Examples include polyethylene, polypropylene, ethylene-propylene copolymer, polybutene, ethylene-butene copolymer, and ethylene-octene copolymer. The copolymer may be either a random copolymer or a block copolymer. (2
The α-olefin copolymer may be a mixture of these. It may also contain an olefin-based thermoplastic elastomer such as a copolymer rubber of two or more types of α-olefins, or a copolymer of an α-olefin and another monomer. These copolymer rubbers include:
Examples of suitable polyolefin resins include ethylene-propylene copolymer rubber (EPR), ethylene-butene copolymer rubber (EBR), ethylene-octene copolymer rubber, and ethylene-propylene-diene copolymer rubber (EPDM). Among these polyolefin resins, homo- or block polypropylene is preferred, and in particular, syndiotactic polypropylene homopolymer, which has a crystalline melting peak temperature of 155°C by DSC, is preferred.
When the above propylene-ethylene block resin is used, the heat resistance of the resulting composition is increased.

In addition, the melt flow rate (JIS K
6758: 230°C, 2.16 kg load) is preferably in the range of 0.1 to 150 g/10 min. The polymerization method for polyolefin resins may be any of the conventionally known methods, such as transition polymerization, radical polymerization, and ionic polymerization.

In the composition of the present invention containing the hydrogenated block copolymer and the polyolefin resin, (1) the proportion of the hydrogenated block copolymer is 1 to 95 parts by weight, preferably 3 to 10 parts by weight.
(2) The proportion of polyolefin resin is 99 to 5 parts by weight, preferably 97 to 10 parts by weight, more preferably 95
If the proportions of the polyolefin resin and the hydrogenated block copolymer are outside this range, the performance aimed at by the present invention cannot be obtained.

In the present invention, the preferred blending ratios for the impact-resistant resin composition are (1) 99 to 50 parts by weight, preferably 97 to 60 parts by weight, and more preferably 95 to 65 parts by weight of the polyolefin resin, (2) 1 to 50 parts by weight of the hydrogenated block copolymer,
The amount is preferably 3 to 40 parts by weight, more preferably 5 to 35 parts by weight. If the proportion of the hydrogenated block copolymer is less than 1 part by weight, the impact strength will be low, and if it exceeds 50 parts by weight, the rigidity will be deteriorated.

In the present invention, it is recommended that the suitable blending ratios for the flexible resin composition are (1) 99 to 5 parts by weight, preferably 95 to 10 parts by weight, and more preferably 90 to 15 parts by weight of polyolefin resin, and (2) 1 to 95 parts by weight, preferably 5 to 90 parts by weight, and more preferably 10 to 85 parts by weight of hydrogenated block copolymer. If the proportion of the hydrogenated block copolymer is less than 1 part by weight, the flexibility of the flexible resin composition will be poor, and if it exceeds 95 parts by weight, the blocking resistance of a film formed from the flexible resin composition will be deteriorated.

Furthermore, in the present invention, it is recommended that the suitable blending ratios for the flexible resin composition are (1) 20 to 95 parts by weight, preferably 40 to 90 parts by weight, and more preferably 50 to 85 parts by weight of the hydrogenated block copolymer, and (2) 80 to 5 parts by weight, preferably 60 to 10 parts by weight, and more preferably 50 to 15 parts by weight of the polyolefin resin. If the proportion of the hydrogenated block copolymer is less than 20 parts by weight, the flexibility of the flexible resin composition will be poor, and if it exceeds 95 parts by weight, the hardness and rigidity will decrease.

In the present invention, when obtaining a flexible resin composition, it is recommended to use 5 to 300 parts by weight, preferably 10 to 200 parts by weight, and more preferably 15 to 150 parts by weight of a non-aromatic rubber softener per 100 parts by weight of the hydrogenated block copolymer (1) described above. If the amount of non-aromatic rubber softener is less than 5 parts by weight, the flexibility of the flexible resin composition will be poor, and if it exceeds 300 parts by weight, the mechanical strength will decrease. Examples of non-aromatic rubber softeners include mineral oil-based softeners, generally known as paraffinic or naphthenic oils, with paraffinic oils being preferred in terms of impact resilience and heat resistance stability.

The resin composition of the present invention can contain any additives as needed. The type of additive is not particularly limited as long as it is one commonly used in resin formulations, but examples include inorganic fillers such as silica, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium sulfate, barium sulfate, talc, mica, silicic acid (white carbon), and titanium oxide; pigments such as carbon black and iron oxide; lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, and ethylene bisstearamide; mold release agents; plasticizers such as organic polysiloxanes and mineral oils; antioxidants such as hindered phenol antioxidants and phosphorus-based heat stabilizers; hindered amine light stabilizers, benzotriazole ultraviolet absorbers, flame retardants, antistatic agents; reinforcing agents such as organic fibers, glass fibers, carbon fibers, and metal whiskers; colorants; other additives; and mixtures thereof.

In the impact-resistant resin composition of the present invention, the amount of inorganic filler used is 50 parts by weight or less, preferably 5 to 40 parts by weight, based on 100 parts by weight of the total amount of the polyolefin resin and the hydrogenated block copolymer, in order to balance impact resistance and rigidity.
The amount of inorganic filler used in the flexible resin composition is preferably in parts by weight.
It is recommended that the amount be 500 parts by weight or less, preferably 10 to 300 parts by weight, more preferably 30 to 200 parts by weight, per 100 parts by weight of the hydrogenated block copolymer, from the viewpoints of flexibility, mechanical strength and moldability.

Next, the tackifier of component (2) used in the present invention is not particularly limited in type, and may be any of the following:
Examples of known tackifying resins include rosin-based terpene resins, hydrogenated rosin-based terpene resins, coumarone resins, phenolic resins, terpene-phenolic resins, aromatic hydrocarbon resins, and aliphatic hydrocarbon resins, and two or more of these tackifiers can be used in combination. Specific examples of tackifiers that can be used include those described in "Rubber and Plastic Compounding Chemicals" (compiled by Rubber Digest Co., Ltd.). The amount of tackifier used is in the range of 20 to 400 parts by weight, preferably 50 to 350 parts by weight, per 100 parts by weight of component (1). If the amount used is less than 20 parts by weight, it is difficult to impart tack to the adhesive composition, and if it exceeds 400 parts by weight, the holding power of the adhesive composition will decrease, and in either case, the adhesive properties will tend to be impaired.

In the present invention, known naphthenic and paraffinic process oils and mixed oils thereof can be used as softeners in the adhesive composition.
By adding a softener, the viscosity of the adhesive composition is reduced, thereby improving the processability and adhesiveness.
It is used in the range of 0 to 200 parts by weight relative to 0 parts by weight of the hydroxybenzoate. If it exceeds 200 parts by weight, the holding power of the adhesive composition tends to be significantly impaired.

Suitable stabilizers for use in the resin composition or adhesive composition of the present invention include, for example, 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate, 2,2'-methylenebis(4-methyl-6-t-butylphenol), ...
, 2'-methylenebis(4-ethyl-6-t-butylphenol), 2,4-bis[(octylthio)methyl]-0-cresol, 2-t-butyl-6-(3-
t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2,4-di-t-amyl-6-[1-(3,5-di-t-amyl-2
hindered phenol-based antioxidants such as 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)]acrylate and 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)]acrylate; sulfur-based antioxidants such as dilauryl thiodipropionate, lauryl stearyl thiodipropionate pentaerythritol-tetrakis(β-lauryl thiopropionate); tris(nonylphenyl)
Examples of the light stabilizer include phosphorus-based antioxidants such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(
2'-hydroxy-3',5'-t-butylphenyl)benzotriazole, 2
benzotriazole-based ultraviolet absorbers such as 2-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole;
Examples of such an ultraviolet absorber include benzophenone-based ultraviolet absorbers such as 4-methoxybenzophenone, and hindered amine-based light stabilizers.

If necessary, pigments such as red iron oxide and titanium dioxide; waxes such as paraffin wax, microcrystalline wax and low molecular weight polyethylene wax; amorphous polyolefin or low molecular weight vinyl aromatic thermoplastic resin; natural rubber; and synthetic rubbers such as polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber, chloroprene rubber, acrylic rubber, isoprene-isobutylene rubber, polypentenamer rubber, and styrene-isoprene block copolymers other than those of the present invention may be added to the resin composition or adhesive composition of the present invention.

The method for producing the resin composition of the present invention is not particularly limited, and known methods can be used. For example, a melt-kneading method using a general mixer such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a co-kneader, or a multi-screw extruder, or a method in which the components are dissolved or dispersed and mixed and then the solvent is removed by heating, etc. In the present invention, the melt-mixing method using an extruder is preferred from the viewpoints of productivity and good kneading ability.

The method for producing the adhesive composition of the present invention is not particularly limited, and
A known method can be used, for example, by uniformly mixing the components under heating using a known mixer, kneader, or the like.

EXAMPLES The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these examples in any way.

1. Polyolefin Resin Composition (I) Components Used and Their Preparation (1) Block Copolymer *Analysis of Block Copolymer Block copolymer analysis was performed according to the following method.

1) Styrene content Measured using an infrared spectrophotometer (JASCO Corporation, FT/IR-410).

2) Vinyl content: Measured using an infrared spectrophotometer (FT/IR-410, manufactured by JASCO Corporation) and calculated by the Hampton method.

3) Molecular Weight: GPC (the apparatus was manufactured by Waters, and the column was ZORBA manufactured by DuPont)
X is a combination of two PSM1000-S and one PSM60-S, for a total of three. Tetrahydrofuran was used as the solvent, and the measurement was carried out at a temperature of 35°C. The molecular weight is
The number average molecular weight is calculated by using the molecular weight of the peak in the chromatogram and a calibration curve (created using the peak molecular weight of the standard polystyrene) obtained from the measurement of commercially available standard polystyrene. When there are multiple peaks in the chromatogram, the molecular weight is calculated as follows:
This refers to the average molecular weight calculated from the molecular weight of each peak and the composition ratio of each peak (calculated from the area ratio of each peak in the chromatogram).

4) Hydrogenation Rate H and Hydrogenation Rate of Vinyl Bond The hydrogenation rate H and the hydrogenation rate of vinyl bond were measured using a nuclear magnetic resonance spectrometer (manufactured by BRUKER, DPX-400).

*Preparation of Block Copolymer The hydrogenated block copolymer used in the polyolefin resin composition was prepared by the following method.

A 100 L capacity autoclave equipped with a stirrer and a jacket was washed, dried, and purged with nitrogen, and a cyclohexane solution containing 10 parts by weight of purified styrene was added thereto. Then, n-butyllithium and tetramethylethylenediamine were added thereto, and the mixture was stirred.
After polymerization at 70° C. for 1 hour, a cyclohexane solution containing 80 parts by weight of previously purified butadiene was added and polymerized for 1 hour, and then a cyclohexane solution containing 10 parts by weight of styrene was added and polymerized for 1 hour.

A portion of the resulting block copolymer solution was sampled and diluted with octadecyl-3-
0.3 parts by weight of (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by weight of the block copolymer, and then the solvent was removed by heating (the resulting copolymer was designated Polymer 1). Polymer 1 had a styrene content of 2.
0% by weight, and the amount of 1,2-vinyl bonds in the polybutadiene part was 50% by weight.

Next, the remaining block copolymer solution was hydrogenated at a temperature of 7°C using di-p-trisbis(1-cyclopentadienyl)titanium and n-butyllithium as hydrogenation catalysts.
Hydrogenation was carried out at 0°C, and a portion of the polymer solution was sampled to obtain Polymer 2. Polymer 2 had a total hydrogenation rate of unsaturated double bonds based on butadiene, H(
The hydrogenation rate (hereinafter referred to as "hydrogenation rate H") was 40%, and the melt flow rate was 90 g/10 min.
The hydrogenation rate H was controlled by measuring the amount of hydrogen gas supplied with a flow meter and stopping the gas supply when the target hydrogenation rate was reached. The remaining polymer solution was hydrogenated again to obtain copolymer solutions of polymers 3 and 4. Polymer 3 had a hydrogenation rate H of 65% and a melt flow rate of 40 g/10 min. Polymer 4 had a hydrogenation rate H of 97% and a melt flow rate of 12 g/10 min.

The stabilizer was added to each copolymer solution in the same manner as for Polymer 1, and then the solvent was removed by heating to produce Polymers 2, 3, and 4. The polymer structures of each sample are shown in Table 1.

Table 1 also shows the hydrogenation rate of the vinyl bond of each polymer.

Polymerization was carried out in the same manner as in Example 1, except that the amounts of n-butyllithium and tetramethylethylenediamine added were changed, to obtain a block copolymer.

This block copolymer solution was hydrogenated in the same manner as above to obtain polymer 5.
The polymer structures of these samples are shown in Table 1.

Polymerization was carried out in the same manner as in the above, except that the amount of tetramethylethylenediamine added was increased and the polymerization temperature was set to 20°C, to obtain a block copolymer having a styrene content of 20% by weight and a 1,2-vinyl bond content of 85% by weight in the polybutadiene moiety.

This block copolymer solution was hydrogenated in the same manner as above to obtain polymer 8.
The polymer structure of this sample is shown in Table 1.

Block copolymers were obtained in the same manner as in Example 1, except that the amounts of styrene and butadiene added, and the amounts of n-butyllithium and tetramethylethylenediamine added were changed. Each of the obtained block copolymers was hydrogenated in the same manner as in Example 1,
Polymers 9 to 11 were prepared. The polymer structures of the samples are shown in Table 1.

A 100 L capacity autoclave equipped with a stirrer and a jacket was washed, dried, and purged with nitrogen. A cyclohexane solution containing 10 parts by weight of previously purified butadiene was added, and then n-butyllithium and tetramethylethylenediamine were added and the mixture was stirred for 7 hours.
After polymerization for 1 hour at 0°C, a cyclohexane solution containing 17.5 parts by weight of pre-purified styrene was added. After polymerization for 1 hour, a cyclohexane solution containing 55 parts by weight of pre-purified butadiene was added and polymerization continued for 1 hour, after which another 17.5 parts by weight of styrene was added.
A cyclohexane solution containing 5 parts by weight of the copolymer was added and polymerized for 1 hour.

Thereafter, hydrogenation was carried out in the same manner as in step 1 to prepare Polymer 12. The polymer structure of the obtained sample is shown in Table 1.

Block copolymers were obtained in the same manner as in (1), except that the amounts of n-butyllithium and tetramethylethylenediamine added were changed. Hydrogenation was then carried out in the same manner as in (1), to produce polymers 13 and 14. The polymer structures of the obtained samples are shown in Table 1.

A 100 L capacity autoclave equipped with a stirrer and a jacket was washed, dried, and purged with nitrogen, and a cyclohexane solution containing 15 parts by weight of purified styrene was added thereto. Then, n-butyllithium and tetramethylethylenediamine were added thereto.
After polymerization at 70° C. for 1 hour, a cyclohexane solution containing 70 parts by weight of pre-purified isoprene was added and polymerization was continued for 1 hour, and then a cyclohexane solution containing 15 parts by weight of isoprene was added and polymerization was continued for another 1 hour.

Next, this block copolymer solution was used to hydrogenate di-p-trisbis(1-cyclopentadienyl)titanium and dibutylmagnesium at a temperature of 7
Hydrogenation was carried out at 0° C. to obtain Polymer 15. The polymer structure of the obtained sample is shown in Table 1.

A 100 L capacity autoclave equipped with a stirrer and a jacket was washed, dried, and purged with nitrogen, and a cyclohexane solution containing 6.5 parts by weight of pre-purified styrene was charged thereinto. Next, n-butyllithium and tetramethylethylenediamine were added and polymerized at 70° C. for 1 hour, followed by addition of a cyclohexane solution containing 87 parts by weight of pre-purified butadiene and polymerization for 1 hour, after which a cyclohexane solution containing 6.5 parts by weight of styrene was further added and polymerization for 1 hour.

Thereafter, hydrogenation was carried out in the same manner as above to prepare polymer 16 and polymer 17.
The polymer structures of the obtained samples are shown in Table 1.

Block copolymers were obtained in the same manner as in (1) except that the amounts of n-butyllithium and tetramethylethylenediamine added were changed. Hydrogenation was then carried out in the same manner as in (1) to produce polymers 18 and 19. The polymer structures of the obtained samples are shown in Table 1.

(2) Polyolefin Resin (2-1) Commercially Available Polypropylene Resin: MK711 (Montel S.D.K. Sunrise Co., Ltd.) <Block PP> (2-2) Commercially Available Polypropylene Resin: PC600S (Montel S.D.K. Sunrise Co., Ltd.) <Homo PP> (2-3) Commercially Available High-Density Polyethylene Resin: Suntec J301 (Asahi Kasei Corporation)
(3) Talc: Microace P-4 (Nippon Talc Co., Ltd.) (II) Preparation of Resin Composition and Measurement of Physical Properties <Impact-Resistant Resin Composition> Each of components (1), (2) and (3) was mixed in the proportions shown in Table 2, and 3
The mixture was melt-kneaded at 220° C. using a 100 mm twin-screw extruder and pelletized. The resulting pellets were injection-molded at 220° C., and the following properties 1) to 5) were measured.

The measurement standards and test methods for the physical properties shown in the examples and comparative examples are as follows:
1) Processability: The melt flow (230° C./2.16 kg load) of pellets of the resin composition was measured in accordance with JIS K6758 and used as an index.

2) Rigidity: A bending test was performed on an injection-molded test piece in accordance with ASTM D790.
The flexural modulus was measured.

3) Impact resistance: Izod impact strength (notched) was measured at -30°C in accordance with JIS K7110.

4) Tensile elongation: The tensile elongation at break of the injection-molded test specimens was measured according to ASTM D638. The pulling speed was 20 mm/min.

5) Heat aging resistance: Injection-molded test pieces of the resin composition were conditioned at 135°C for 200 hours. Thereafter, the tensile elongation at break was measured in the same manner as in 4) and the retention rate relative to the elongation of an unconditioned sample was determined. The higher the retention rate, the better the heat aging resistance was judged to be.

The results of Examples 1 to 4 and Comparative Examples 1 to 11 are shown in Table 2.

Examples 1 to 4 and Comparative Examples 1 to 11 Table 2 shows that Example 1 and Comparative Examples 1 to 7 contain 10 parts by weight of hydrogenated block copolymer as component (1), 80 parts by weight of polypropylene as component (2-1),
The physical properties of the resin composition containing 10 parts by weight of talc are shown in Table 1.
As Comparative Examples 1 to 4 and Comparative Examples 8 to 11, the physical properties of resin compositions containing 15 parts by weight of hydrogenated block copolymer as component (1), 65 parts by weight of polypropylene (2-1) as component (2), and 20 parts by weight of talc are shown.

The resin composition of the present invention has low-temperature impact resistance, moldability (fluidity), heat aging resistance,
It is clear that this is a composition with an excellent balance in terms of rigidity.

Example 5 10 parts by weight of hydrogenated block copolymer of polymer 3 as component (1), component (
The physical properties of a thermoplastic resin composition containing 90 parts by weight of the high-density polyethylene resin (2-3) were measured. The resulting resin composition was well-balanced in terms of low-temperature impact resistance, moldability (fluidity), heat aging resistance, and rigidity.

<Soft Resin Composition> Each component (1) and component (2-2) were blended in the proportions shown in Table 3, and the blend was melt-kneaded at 230° C. using a 30 mm single-screw sheet extruder to form a sheet. The obtained sheet (80 μm) was used to measure the following various properties 1) to 3).

The measurement standards and test methods for the physical properties shown in the examples and comparative examples are as follows:
1) Processability: The melt flow rate (230°C/2.16 kg load) of a sheet of the resin composition was measured in accordance with JIS K 6758. The larger the value, the better the processability was judged to be.

2) Flexibility: A tensile test was carried out at a tensile speed of 2 mm/min in accordance with JIS K7127. The sheet was cut into a shape of 20 mm wide x 200 mm long, and the tensile modulus at 300% elongation was measured as M300%. The smaller the value, the better the flexibility.

3) Transparency: Haze was measured using a haze meter (manufactured by Nippon Denshoku) in accordance with JIS K 7105. The smaller the value, the better the transparency.

The results of Example 6 and Comparative Examples 12 to 15 are shown in Table 3 below.

Table 3 shows the physical properties of thermoplastic resin compositions containing 20 parts by weight of hydrogenated block copolymer (1) and 80 parts by weight of polypropylene (2-2) as component (2) as Example 6 and Comparative Examples 12 to 15.
2-2) showed the physical properties of 100% polypropylene by weight.

It is clear that the resin composition of the present invention is a composition excellent in flexibility, transparency, and moldability (fluidity).

2. Adhesive Composition (I) Components Used and Their Preparation (1) Block Copolymer *Analysis of Block Copolymer Block copolymer analysis was performed according to the following method.

1) Styrene content: Styrene content was measured using an ultraviolet spectrophotometer (Hitachi UV200) at 262n
The absorption intensity was calculated from m.

2) Peak molecular weight and composition ratio: GPC (the apparatus was manufactured by Waters, and the columns were two ZORBAX PSM1000-S columns and one PSM60-S column manufactured by DuPont)
The solvent used was tetrahydrofuran, and the measurement was carried out at a temperature of 35°C. The peak molecular weight was determined by measuring the molecular weight of the peak in the chromatogram using a calibration curve (created using the peak molecular weight of the standard polystyrene) obtained from the measurement of a commercially available standard polystyrene. In addition, when component (1) was mixed with component (1-A) and component (
The composition ratio of the compound consisting of 1-B) was determined from the area ratio of each peak in the chromatogram.

3) Vinyl bonds and hydrogenation rate Measured using a nuclear magnetic resonance spectrometer (BRUKER DPX-400).

*Preparation of Block Copolymer The hydrogenated block copolymer used in the adhesive composition was prepared by the following method.

A 100 L capacity autoclave equipped with a stirrer and a jacket was washed, dried, and purged with nitrogen, and a cyclohexane solution containing 10 parts by weight of purified styrene was added thereto. Then, n-butyllithium and tetramethylethylenediamine were added thereto, and the mixture was stirred.
After polymerization at 70° C. for 1 hour, a cyclohexane solution containing 80 parts by weight of previously purified butadiene was added and polymerized for 1 hour, and then a cyclohexane solution containing 10 parts by weight of styrene was added and polymerized for 1 hour.

A portion of the resulting block copolymer solution was sampled and diluted with octadecyl-3-
0.3 parts by weight of (3,5-di-t-butyl-4-hydroxyphenyl)propionate was added to 100 parts by weight of the block copolymer, and then the solvent was removed by heating (the resulting copolymer is designated Polymer 20). Polymer 20 had a styrene content of 20% by weight, a 1,2-vinyl bond content of 50% by weight in the polybutadiene portion, and a molecular weight of 105,000.

Next, the remaining block copolymer solution was hydrogenated at a temperature of 7°C using di-p-trisbis(1-cyclopentadienyl)titanium and n-butyllithium as hydrogenation catalysts.
Hydrogenation was carried out at 0°C, and a portion of the polymer solution was sampled to obtain Polymer 21. Polymer 21 had a total hydrogenation rate H of unsaturated double bonds based on butadiene (hereinafter referred to as hydrogenation rate H) of 40%, and a hydrogenation rate of vinyl bonds of 73%. The hydrogenation rate H was controlled by measuring the amount of hydrogen gas supplied with a flow meter and stopping the gas supply when the target hydrogenation rate was achieved. The remaining polymer solution was hydrogenated again to obtain copolymer solutions of Polymers 22 to 24.

The solvent was removed by heating after adding a stabilizer to each copolymer solution, as in the case of polymer 20. The properties of each sample are shown in Table 4.

Polymerization was carried out in the same manner as in Example 1 except that the amounts of n-butyllithium and tetramethylethylenediamine added were changed, to obtain a block copolymer having a styrene content of 20% by weight and a 1,2-vinyl bond content of 14% by weight in the polybutadiene moiety.

This block copolymer solution was hydrogenated in the same manner as above, and polymer 2
The properties of this sample are shown in Table 4.

Polymerization was carried out in the same manner as in the above, except that the amount of tetramethylethylenediamine added was increased and the polymerization temperature was set to 20°C, to obtain a block copolymer having a styrene content of 20% by weight and a 1,2-vinyl bond content of 85% by weight in the polybutadiene moiety.

This block copolymer solution was hydrogenated in the same manner as above, and polymer 2
The properties of this sample are shown in Table 4.

Block copolymers were obtained in the same manner as in (1), except that the amounts of styrene and butadiene added, and the amounts of n-butyllithium and tetramethylethylenediamine added were changed. Each of the obtained block copolymers was hydrogenated in the same manner as in (1), to produce polymers 27 to 29. The properties of each sample are shown in Table 4.

A 100 L capacity autoclave equipped with a stirrer and a jacket was washed, dried, and purged with nitrogen. A cyclohexane solution containing 10 parts by weight of previously purified butadiene was added, and then n-butyllithium and tetramethylethylenediamine were added and the mixture was stirred for 7 hours.
After polymerization for 1 hour at 0°C, a cyclohexane solution containing 17.5 parts by weight of pre-purified styrene was added. After polymerization for 1 hour, a cyclohexane solution containing 55 parts by weight of pre-purified butadiene was added and polymerization continued for 1 hour, after which another 17.5 parts by weight of styrene was added.
A cyclohexane solution containing 5 parts by weight of the copolymer was added and polymerized for 1 hour.

Thereafter, hydrogenation was carried out in the same manner as in the above to prepare polymer 30. The properties of the obtained sample are shown in Table 4.

Block copolymers were obtained in the same manner as in (1) except that the amounts of n-butyllithium and tetramethylethylenediamine added were changed. Hydrogenation was then carried out in the same manner as in (1) to produce polymers 31 and 32. The properties of the obtained samples are shown in Table 4.

A 100 L capacity autoclave equipped with a stirrer and a jacket was washed, dried, and purged with nitrogen, and a cyclohexane solution containing 30 parts by weight of purified styrene was added thereto. Next, n-butyllithium and tetramethylethylenediamine were added, and the mixture was stirred.
After polymerization at 70°C for 1 hour, a cyclohexane solution containing 70 parts by weight of previously purified butadiene was added and polymerization was continued for 1 hour. Thereafter, phenylmethyldichlorosilane was added as a coupling agent to cause coupling, thereby obtaining a mixture of coupled and uncoupled polymers.

Thereafter, hydrogenation was carried out in the same manner as in step 1 to prepare polymers 33 and 34. The properties of the obtained samples are shown in Table 4.

A 100 L capacity autoclave equipped with a stirrer and a jacket was washed, dried, and purged with nitrogen, and a cyclohexane solution containing 35 parts by weight of purified styrene was added thereto. Then, n-butyllithium and tetramethylethylenediamine were added thereto.
After polymerization at 70°C for 1 hour, a cyclohexane solution containing 65 parts by weight of previously purified butadiene was added and polymerization was continued for 1 hour, followed by the addition of silica tetrachloride as a coupling agent to effect coupling, thereby obtaining a mixture of coupled and uncoupled polymers.

Thereafter, hydrogenation was carried out in the same manner as in step 1 to prepare polymers 35 and 36. The properties of the obtained samples are shown in Table 4.

The specific hydrogenated block copolymer (Polymer 37) described in Example 3 of Japanese Patent Publication No. 5-69874 was obtained by the method disclosed in the publication.
The styrene content was 20% by weight, the amount of 1,2-vinyl bonds in the polybutadiene portion was 35% by weight, the hydrogenation rate H was 45%, and the hydrogenation rate of vinyl bonds was 80%.

The mixture was dried and purged with nitrogen, and a cyclohexane solution containing 15 parts by weight of pre-purified styrene was added. Then, n-butyllithium and tetramethylethylenediamine were added, and polymerization was carried out for 1 hour at 70°C. After that, a cyclohexane solution containing 80 parts by weight of pre-purified isoprene was added, and polymerization was carried out for 1 hour. Then, a cyclohexane solution containing 15 parts by weight of styrene was added, and polymerization was carried out for another 1 hour. The obtained block copolymer had a styrene content of 3.
The total amount of vinyl bonds in the 0 wt % polyisoprene portion was 40 wt %.

Next, this block copolymer solution was used to hydrogenate di-p-trisbis(1-cyclopentadienyl)titanium and dibutylmagnesium at a temperature of 7
Hydrogenation was carried out at 0° C. to obtain Polymer 38. Polymer 38 had a hydrogenation rate H of 55%, a hydrogenation rate of vinyl bonds of 95%, and a molecular weight of 120,000.

(2) Tackifier (2-1) Commercially available alicyclic petroleum resin: Alcon M100 (manufactured by Arakawa Chemical Co., Ltd.) (2-2) Commercially available aliphatic petroleum resin: Escolez 1310 (manufactured by Esso Chemical Co., Ltd.)
(3) Paraffin-based process oil: PW-90 (Idemitsu Kosan Co., Ltd.) (II) Measurement of physical properties of adhesive compositions The measurement standards and test methods for the adhesive compositions shown in the examples and comparative examples are as follows.

1) Melt Viscosity The melt viscosity of each adhesive composition at 160°C was measured using a Brookfield viscometer.

2) Softening point: According to JIS-K2207, a sample is filled into a specified ring, and the ring is supported horizontally in water. A 3.5 g ball is placed in the center of the sample, and the liquid temperature is raised at a rate of 5°C/min.
The temperature was measured when the weight of the ball caused the sample to touch the bottom plate of the ring stand.

3) Rate of change in melt viscosity Using a Brookfield viscometer, the melt viscosity of the adhesive composition immediately after kneading at 180°C was taken as η0, and the adhesive composition was left in an atmosphere at a temperature of 180°C for 4 hours.
When the melt viscosity at 180°C after standing for 8 hours was taken as η1, the following rate of change in melt viscosity was determined and used as a measure of thermal stability.

Next, the adhesive composition was taken out in a molten state and coated onto a polyester film with an applicator to a thickness of 50 micrometers to prepare an adhesive tape sample, and the adhesive properties were measured by the following method.

4) Loop tack Measurement was carried out using a loop-shaped sample of 250 mm long x 15 mm wide and a stainless steel plate as the adherend, with a contact area of 15 mm x 50 mm, adhesion time of 3 seconds, and adhesion and peeling speed of 500 mm/min.

5) Adhesion strength: A 25 mm wide sample was attached to a stainless steel plate and peeled off at a speed of 300 mm/m.
The 180 degree peel force was measured in inches.

6) Holding power The holding power is measured in accordance with JIS Z-1524 by applying a 25mm x 25m diameter adhesive tape to a stainless steel plate.
An adhesive tape was applied so that the area of 100 mm was in contact with the adhesive tape, and a load of 1 kg was applied at 60° C., and the time until the adhesive tape slipped off was measured.

The results of Examples 7 to 17 and Comparative Examples 16 to 26 are shown in Table 5.

Examples 7 to 14 and Comparative Examples 16 to 24: 100 parts by weight of the block copolymer of component (1), 250 parts by weight of (2-1) as a tackifier of component (2), and paraffinic process oil PW as a softener.
The block copolymers were blended in a ratio of 60 parts by weight of 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate and 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate as a stabilizer per 100 parts by weight of the block copolymer, and the results of measuring the physical properties of each adhesive composition are shown in Table 5.

As is clear from Table 5, the adhesive compositions falling within the ranges specified in the present invention exhibit good melt viscosity, softening point, loop tack, adhesive strength and holding power, and also have a small rate of change in melt viscosity, providing well-balanced adhesive properties.

Examples 15 to 17 and Comparative Examples 25 and 26 Adhesive compositions were prepared in the same manner as in Example 7 except that the blending amounts of the tackifier and softener in Example 7 were changed, and the adhesive properties thereof are shown in Table 5.

Examples 18 to 21 Adhesive compositions were prepared in the same manner as in Example 7, except that Escolez 1310 (2-2) was used as the tackifier (2), and the adhesive properties thereof were as follows:
Shown in 6.

Comparative Example 27 An adhesive composition was prepared in the same manner as in Example 7, except that Polymer 37 was used as the block copolymer. The obtained adhesive composition had a larger rate of change in melt viscosity than those of Examples 7 and 9, and was inferior in long-term storage stability at high temperatures, because the hydrogenation rate of the vinyl bond of Polymer 37 did not satisfy the requirements of the present invention.

Example 22 An adhesive composition was prepared in the same manner as in Example 18, except that Polymer 38 was used as the block copolymer. The obtained adhesive composition exhibited good melt viscosity, softening point, loop tack, adhesive strength and holding power, and also had a small rate of change in melt viscosity, so that it had well-balanced adhesive properties.

<Industrial Applicability> The hydrogenated block copolymer of the present invention exhibits excellent performance in modifying polyolefin resins. Furthermore, the polyolefin resin composition of the present invention has excellent impact resistance (
The polyolefin resin composition exhibits an excellent balance of low-temperature impact resistance, rigidity, moldability, and heat aging resistance. It is also possible to obtain a polyolefin resin composition with excellent transparency, flexibility, and moldability. By utilizing these characteristics, the polyolefin resin can be processed into molded products of various shapes by injection molding, extrusion molding, and other methods, and can be used for automobile parts (automobile interior and exterior materials), various containers such as food packaging containers, home appliances, medical device parts, industrial parts, toys, and the like.

Furthermore, the adhesive composition of the present invention exhibits good melt viscosity, softening point, loop tack, adhesive strength and holding power, and has a small rate of change in melt viscosity, providing an excellent balance of adhesive properties. Utilizing these characteristics, the composition can be used for various adhesive tapes and labels, pressure-sensitive thin plates, pressure-sensitive sheets, backing adhesives for fixing various lightweight plastic molded products, backing adhesives for fixing carpets, backing adhesives for fixing tiles, etc., and is particularly useful for adhesive tapes and labels.

───────────────────────────────────────────────────── (Note) This publication is based on the publication published internationally by the International Bureau of Patents (WIPO). The effect of the international publication of the Japanese patent application (Japanese utility model registration application) related to this publication arises pursuant to Article 184-10, Paragraph 1 of the Patent Act (Article 48-13, Paragraph 2 of the Utility Model Act) and is unrelated to this publication.

Claims (8)

[Claims] [Claim 1] (1) A hydrogenated block copolymer having at least one polymer block mainly composed of a vinyl aromatic hydrocarbon and at least one polymer block mainly composed of a conjugated diene compound, in which the vinyl bond content V (%) based on the conjugated diene compound is 37% or more but less than 70%, wherein: (a) a total hydrogenation rate H(
%) satisfies the following relationship: V<H<1.25×V+10 50≦H<80 (b) A hydrogenated block copolymer having a hydrogenation rate of vinyl bonds of 82% or more. 2. A block copolymer composition comprising: (1) the hydrogenated block copolymer according to claim 1; and (2) a polyolefin resin. [Claim 3] The block copolymer composition of claim 2, wherein the composition comprises 1 to 50 parts by weight of component (1) and 99 to 50 parts by weight of component (2), relative to 100 parts by weight of the total weight of components (1) and (2), and component (1) further satisfies the following requirements: (c) a vinyl aromatic hydrocarbon content of 5 to 50% by weight, and (d) a melt flow rate of 0.5 to 100 g/10 min. 4. The composition of claim 1, wherein the composition comprises 1 to 95 parts by weight of component (1) and 99 to 5 parts by weight of component (2) per 100 parts by weight of the total weight of component (1) and component (2),
The block copolymer composition according to claim 2, wherein component (1) further satisfies the following requirements: (c) a vinyl aromatic hydrocarbon content of 5 to 35% by weight; and (d) a number average molecular weight of more than 30,000 and less than 330,000. 5. The composition according to claim 1, wherein the total weight of the components (1) and (2) is 100 parts by weight, and the total weight of the components (1) and (2) is 20 to 95 parts by weight of the component (1) and 80 to 5 parts by weight of the component (2), and further
3. The block copolymer composition according to claim 2, comprising, per 100 parts by weight of component (1), (3) 5 to 300 parts by weight of a non-aromatic rubber softener and (4) 500 parts by weight or less of an inorganic filler, wherein component (1) further satisfies the following requirements: (c) a vinyl aromatic hydrocarbon content of 5 to 50% by weight, and (d) a number average molecular weight of 50,000 to 1,000,000. (1) A hydrogenated block copolymer having at least one polymer block mainly composed of a vinyl aromatic hydrocarbon and at least one polymer block mainly composed of a conjugated diene compound, in which the vinyl bond content V (%) based on the conjugated diene compound is 30% or more and less than 70%, wherein: (a) a total hydrogenation rate H(
%) satisfies the following relationship: V<H<2×V+10 30≦H<80 (b) 100 parts by weight of a hydrogenated block copolymer having a hydrogenation rate of vinyl bonds of 82% or more, and (2) 20 to 400 parts by weight of a tackifier (based on 100 parts by weight of component (1)).
A block copolymer composition comprising: [Claim 7] The block copolymer composition according to claim 6, wherein component (1) further satisfies the following requirements: (c) a vinyl aromatic hydrocarbon content of 5 to 60% by weight, and (d) a peak molecular weight of 50,000 to 300,000. [Claim 8] Component (1) is (1-A) a hydrogenated block copolymer having one polymer block mainly composed of a vinyl aromatic hydrocarbon and one polymer block mainly composed of a conjugated diene compound, in which the vinyl bond content V (%) based on the conjugated diene compound is 30% or more and less than 70%, and (a) a total hydrogenation rate H(
%) satisfies the following relational expressions: V<H<2×V+10 30≦H<80 (b) a hydrogenation rate of vinyl bonds of 82% or more; (c) a content of vinyl aromatic hydrocarbons of 5 to 60% by weight; (1-B) a hydrogenated block copolymer having at least two polymer blocks mainly composed of vinyl aromatic hydrocarbons and at least one polymer block mainly composed of a conjugated diene compound,
A hydrogenated block copolymer having a vinyl bond content V (%) based on a conjugated diene compound of 30% or more and less than 70%, wherein: (a) a total hydrogenation rate H(
7. The block copolymer composition according to claim 6, comprising 80 to 10% by weight of a hydrogenated block copolymer having a vinyl aromatic hydrocarbon content of 5 to 60% by weight, wherein the average molecular weights of components (1-A) and (1-B) are 50,000 to 300,000, and wherein the hydrogenation rate of vinyl bonds is 82% or more and the content of vinyl aromatic hydrocarbons is 5 to 60% by weight.