JP5058764B2 - CROSS COPOLYMER MANUFACTURING METHOD, OBTAINED CROSS COPOLYMER, AND USE THEREOF - Google Patents

Description

The present invention relates to a method for producing a specific cross copolymer having excellent transparency and low film anisotropy, the resulting cross copolymer, and a composition thereof.

An ethylene-styrene (aromatic vinyl compound) copolymer is known (Patent Document 1). The copolymer exhibits properties as an elastomer, further exhibits mechanical properties similar to that of soft vinyl chloride, and can have functionality such as oil resistance. Furthermore, an ethylene-styrene copolymer having isotactic stereoregularity in an alternating structure of ethylene and styrene contained in the copolymer is also known (Patent Document 2). Since this copolymer has limited crystallinity (microcrystallinity) based on an alternating structure compared to a copolymer without stereoregularity, it further improves mechanical properties and functions such as heat resistance and oil resistance. There is a feature that improves.
In a statistical copolymer (so-called random copolymer) whose copolymerization format is described by Bernoulli, primary, or second-order Markov statistics, the crystallinity derived from the ethylene chain determines its heat resistance in a relatively low styrene content region. is doing. In ethylene-styrene copolymers, transparency and softness are increased by copolymerization of styrene monomers, and vinyl chloride-like physical properties (for example, scratch resistance and solvent resistance) are imparted, but derived from ethylene chain The crystallinity to be reduced is reduced, and the melting point (heat resistance) is significantly lowered. For this reason, the ethylene-styrene copolymer in this composition range has a drawback that the heat resistance is essentially insufficient and the compatibility with the styrene polymer is insufficient. In addition, the mechanical properties are more similar to soft PVC compared to olefin polymers such as LLDPE, but more similar mechanical properties to soft PVC are required.

Therefore, a method of copolymerizing a small amount of divinylbenzene with an ethylene-styrene copolymer and introducing a heterogeneous polymer chain by anionic polymerization through the vinyl group of the divinylbenzene unit, a method for producing a so-called cross copolymer has been proposed. (Patent Document 3). By this method, all of the styrene monomer in the polymerization solution is easily incorporated into the polymer, and a very efficient polymerization method is provided. The resulting polymer (cross copolymer) is also an ethylene-styrene copolymer. The heat resistance is also improved up to about 100 ° C. However, any of the cross copolymers described in the examples are opaque.
Japanese Patent No. 2623070 JP-A-9-309925, JP-A-11-130808 No. 00/037517

The present invention improves the heat resistance and compatibility of a conventional ethylene-aromatic vinyl compound copolymer, and further, a novel cross copolymer having excellent transparency and less film anisotropy compared to a conventional cross copolymer. It is providing the manufacturing method of a coalescence, the obtained cross-copolymer, and its resin composition.

The present invention relates to the copolymerization of ethylene monomer, aromatic vinyl compound monomer and aromatic polyene at a polymerization temperature of 80 ° C. or more and 150 ° C. or less using a single site coordination polymerization catalyst composed of a specific transition metal compound and a co-catalyst. The aromatic vinyl compound unit content is 5 mol% or more and less than 15 mol%, preferably 9 mol% or more and less than 15 mol%, the aromatic polyene unit content is 0.01 mol% or more and 3 mol% or less, and the remainder is ethylene unit. The content of ethylene-aromatic vinyl compound-aromatic polyene copolymer is synthesized, and then, as an anionic polymerization step, the ethylene-aromatic vinyl compound-aromatic polyene copolymer and the anionic polymerizable vinyl compound monomer coexist The following is a method for producing a cross copolymer, wherein polymerization is performed using an anionic polymerization initiator.
Moreover, the cross copolymer obtained by this production method is a cross copolymer having a haze of 1 mm thickness sheet of 30% or less, little film anisotropy, and excellent elasticity recovery.

The cross-copolymer obtained by the production method of the present invention is superior in heat resistance and compatibility as compared with a conventional ethylene-aromatic vinyl compound copolymer, and has a film anisotropy as compared with a conventional cross-copolymer. Is small, and has the characteristics of excellent transparency and elastic recovery.

The method for producing a cross-copolymer of the present invention is a production method including a polymerization step comprising a coordination polymerization step and a subsequent anion polymerization step, and is represented by the following general formula (1) as the coordination polymerization step. Copolymerization of ethylene monomer, aromatic vinyl compound monomer and aromatic polyene at a polymerization temperature of 80 ° C. or higher and 150 ° C. or lower using a single site coordination polymerization catalyst composed of a transition metal compound and a cocatalyst, An ethylene vinyl compound unit content of 5 mol% or more and less than 15 mol%, preferably 9 mol% or more and less than 15 mol%, an aromatic polyene unit content of 0.01 mol% or more and 3 mol% or less, and the remainder is ethylene unit content An aromatic vinyl compound-aromatic polyene copolymer is synthesized, and then, as an anionic polymerization step, the ethylene-aromatic vinyl compound-aromatic polymer is synthesized. Presence of ene copolymer and anionic polymerizable vinyl compound monomer, a method for producing a cross-copolymer which comprises polymerizing with an anionic polymerization initiator.


In the formula, A and B may be the same or different, and each is an unsubstituted or substituted benzoindenyl group represented by the general formula (2), (3), or (4), represented by the general formula (5). And a group selected from an unsubstituted or substituted indenyl group. In the following general formulas (2), (3), and (4), R1 to R3 are each hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an alkyl group having 7 to 20 carbon atoms. An aryl group, a halogen atom, an OSiR ₃ group, a SiR ₃ group or a PR ₂ group (wherein R represents a hydrocarbon group having 1 to 10 carbon atoms). R1s, R2s, and R3s may be the same or different from each other, and adjacent R1 and R2 groups may be combined to form a 5- to 8-membered aromatic ring or aliphatic ring. In the following general formula (5), R4 is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, a halogen atom, an OSiR ₃ group, SiR _3. Group or PR ₂ group (R represents a hydrocarbon group having 1 to 10 carbon atoms). R4 may be the same or different from each other.








Y has a bond with A and B, and additionally has hydrogen or a hydrocarbon group having 1 to 15 carbon atoms (may contain 1 to 3 nitrogen, oxygen, sulfur, phosphorus, or silicon atoms) as a substituent. A methylene group or a boron group; The substituents may be different or the same. Y may have a cyclic structure.
X is hydrogen, a hydroxyl group, a halogen, a C1-C20 hydrocarbon group, a C1-C20 alkoxy group, a silyl group having a C1-C4 hydrocarbon substituent, or a C1-C20 It is an amide group having a hydrocarbon substituent. Two Xs may have a bond.
M is zirconium, hafnium, or titanium.

The cross copolymer obtained by this method has a polymer chain composed of an ethylene-aromatic vinyl compound-aromatic polyene copolymer as a main chain and an anion polymerizable monomer unit as a cross chain as the main chain. It is considered to include a structure (cross copolymer structure or segregated star copolymer structure) bonded through an aromatic polyene unit. Although the structure and the ratio of the present cross-copolymer are arbitrary, the cross-copolymer of the present invention is defined as a copolymer obtained by the production method of the present invention.

The composition of the ethylene-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step is such that the aromatic vinyl compound unit content is 5 mol% or more and less than 15 mol%, preferably 9 mol% or more and less than 15 mol%. The polyene unit content is 0.01 mol% or more and 3 mol% or less, and the balance is ethylene units.
For example, if a crystal structure derived from an ethylene chain is present above a certain level, the softness and transparency may be impaired, and the dimensional stability of the molded product, such as shrinkage due to crystallization, may be impaired during molding processing. . Therefore, the composition of the ethylene-aromatic vinyl compound-aromatic polyene copolymer needs to have an aromatic vinyl compound unit content of 5 mol% or more. By being within this composition range, the resulting cross-copolymer has a total crystal fusion heat including ethylene crystallinity and other crystallinity of 100 J / g or less, preferably 60 J / g or less. The total heat of melting of the crystal can be determined from the sum of the peak areas derived from the melting point observed in the range of 50 ° C. to about 140 ° C. by DSC.
Furthermore, by satisfying the condition that the aromatic vinyl compound unit content is less than 15 mol%, there is a feature that a cross-copolymer excellent in elastic recovery and having little film anisotropy can be obtained.
Moreover, the aromatic polyene unit content of the ethylene-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step of the above production method is 0.01 mol% or more and 3 mol% or less. If it is less than 0.01 mol%, the properties as a cross-copolymer are not sufficient, and if it is higher than 3 mol%, the moldability deteriorates. Considering the mechanical properties and moldability of the finally obtained cross-copolymer (evaluable by fluidity and MFR (Melt Flow Rate)), the preferable aromatic polyene unit content is 0.02 mol% or more and 0.5. The most preferred aromatic polyene unit content is 0.03 mol% or more and 0.2 mol% or less. Further, when the aromatic polyene unit content is in the range of 0.03 mol% or more and 0.2 mol% or less, the functionality of the ethylene-aromatic vinyl compound-aromatic polyene copolymer as the main chain is a cross copolymer. It is preferable to make full use of the physical properties. When the aromatic polyene unit content exceeds 0.2 mol%, the average chain length between the aromatic polyene units of the main chain is shortened, and the functionality of the main chain ethylene-aromatic vinyl compound-aromatic polyene copolymer is reduced. May not be fully utilized.
In the coordination polymerization step, polymerization is performed at a polymerization temperature of 80 ° C. or more and 150 ° C. or less using a single site coordination polymerization catalyst composed of a specific transition metal compound and a co-catalyst defined in the present invention. A cross copolymer excellent in transparency having a haze of a 1 mm thickness sheet of 30% or less or a total light transmittance of 75% or more can be obtained.
Furthermore, production of a cross-copolymer using the same copolymer having an ethylene-aromatic vinyl compound-aromatic polyene copolymer weight average molecular weight of 150,000 or less and 30,000 or more obtained in the coordination polymerization step of the present production method Is the method.
By satisfying the above conditions, it is possible to obtain a cross-copolymer having a total crystal fusion heat containing an ethylene chain structure that is not more than a certain level, excellent transparency, little film anisotropy, and excellent elastic recovery. The composition of the ethylene-aromatic vinyl compound-aromatic polyene copolymer can be controlled within the above range by a known general method, but can be most easily achieved by changing the monomer charge composition ratio. .

  Further, in this production method, the mass ratio of the ethylene-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step is 40 with respect to the mass of the cross-copolymer finally obtained through the anionic polymerization step. The production method is characterized in that the content is preferably from 95% by mass to 95% by mass, more preferably from 50% by mass to 95% by mass, and most preferably from 55% by mass to 95% by mass. The cross copolymer obtained by this production method preferably has an A hardness of 50 or more and 95 or less, particularly preferably an A hardness of 60 or more and 85 or less, and an initial elastic modulus of 10 MPa or more and 150 MPa or less. The mass ratio of the ethylene-aromatic vinyl compound-aromatic polyene copolymer obtained in the present coordination polymerization step is, for example, the amount of copolymer produced in the main polymerization step by monitoring the ethylene consumption or polymer concentration and composition. It can be controlled by calculating the mass of the coalescence. In order to reduce the mass ratio, for example, the above monitoring is performed, and the time of the coordination polymerization process is shortened while calculating the mass of the copolymer to be produced, and the anionic polymerization process may be started early. In order to increase the ratio, the polymerization time may be lengthened to delay the start of the anionic polymerization process. Further, an anion polymerizable vinyl compound monomer used in the anion polymerization step may be additionally added at the start of the anion polymerization step or during the step. The mass ratio of the ethylene-aromatic vinyl compound-aromatic polyene copolymer obtained in the present coordination polymerization step can be arbitrarily changed by the additional amount of the anionic polymerizable vinyl compound monomer.

Furthermore, it is a cross-copolymer obtained by this production method, preferably having an initial elastic modulus of 10 MPa or more and 150 MPa or less.
The cross-copolymer obtained by the production method of the present invention is characterized by excellent elasticity recovery.
That is, the film (MD direction) is fixed for 10 minutes in a stretched state of 50%, and then the return rate evaluated by the return rate of elongation when 180 seconds have elapsed after opening is preferably 50% or more, preferably 80%. It has the above characteristics.

Return rate (%) = (Elongation at 50% −Residual elongation after 180 seconds after stress release) / Elongation at 50% × 100

Moreover, the thickness reduction rate by the heat deformation test (75 degreeC, 1.5 kg load) prescribed | regulated to JISC3005 has the characteristics that it is 15% or less, Preferably it is 10% or less.
In addition, as a sheet-like molded body having a thickness of 2 mm, according to JIS K-6264, an H-22 wear wheel is used, and the Taber wear amount when measured under the conditions of 1 kg load and 1000 revolutions is 100 mg or less. Have.
In addition, the Gakushoku wear test was conducted using a friction tester type II (Gakuken / JISL0849) under the conditions of 23 ± 2 ° C. and relative humidity 65 ± 5%. Using a sheet-like molded article having a thickness of 1 mm as a test piece, friction was performed 10,000 times with a white cotton cloth for friction No. 3 (JISL0849 regulation) with a load of 500 g, and the amount of wear was calculated from the change in weight of the test piece. The copolymer obtained by this production method is characterized by a low amount of wear.
Furthermore, the means for forming the film substrate from the copolymer obtained by this production method is not particularly limited, but it is formed by two rolls, calendering or T-die. Usually, if it is this range by shape | molding at the roll temperature of 120-200 degreeC, the melt | fusion of resin is enough and the film which is excellent in an external appearance and secondary workability is obtained. In the molded film having a thickness of 10 to 300 μm, the ratio of the elastic modulus in the parallel (MD) and transverse direction (TD) (MD / TD elastic modulus ratio) is 1.0 or more and 2.0 or less with respect to the film flow direction. Preferably, it has a feature that the anisotropy in the MD / TD direction is small, such as 1.0 or more and 1.7 or less.
Furthermore, the cross-copolymer obtained by the production method of the present invention shows good compatibility with aromatic vinyl compound polymers such as polystyrene and olefin polymers, and these polymers can be mixed to form a polymer. It is also possible to improve the physical properties of-or to use as a compatibilizing agent.

Below, the manufacturing method of this invention is demonstrated in detail.
<Coordination polymerization process>
In the coordination polymerization step of this production method, a single site coordination polymerization catalyst composed of a transition metal compound represented by the following general formula (1) and a cocatalyst is used.


In the formula, A and B may be the same or different, and each is an unsubstituted or substituted benzoindenyl group represented by the general formula (2), (3), or (4), represented by the general formula (5). And a group selected from an unsubstituted or substituted indenyl group. In the following general formulas (2), (3), and (4), R1 to R3 are each hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an alkyl group having 7 to 20 carbon atoms. An aryl group, a halogen atom, an OSiR ₃ group, a SiR ₃ group or a PR ₂ group (wherein R represents a hydrocarbon group having 1 to 10 carbon atoms). R1s, R2s, and R3s may be the same or different from each other, and adjacent R1 and R2 groups may be combined to form a 5- to 8-membered aromatic ring or aliphatic ring. In the following general formula (5), R4 is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, a halogen atom, an OSiR ₃ group, SiR _3. Group or PR ₂ group (R represents a hydrocarbon group having 1 to 10 carbon atoms). R4 may be the same or different from each other.








Y has a bond with A and B, and additionally has hydrogen or a hydrocarbon group having 1 to 15 carbon atoms (may contain 1 to 3 nitrogen, oxygen, sulfur, phosphorus, or silicon atoms) as a substituent. A methylene group or a boron group, most preferably hydrogen or a hydrocarbon group having 1 to 15 carbon atoms as a substituent (may contain 1 to 3 nitrogen, oxygen, sulfur, phosphorus, or silicon atoms) A methylene group having The substituents may be different or the same. Y may have a cyclic structure.
X is hydrogen, a hydroxyl group, a halogen, a C1-C20 hydrocarbon group, a C1-C20 alkoxy group, a silyl group having a C1-C4 hydrocarbon substituent, or a C1-C20 It is an amide group having a hydrocarbon substituent. Two Xs may have a bond.
M is zirconium, hafnium, or titanium.
Furthermore, the transition metal compound represented by the general formula (1) is preferably a racemate.

As the co-catalyst used in the coordination polymerization step of this production method, a known co-catalyst conventionally used in combination with a transition metal compound can be used. As such a co-catalyst, methylaluminoxane (or methyl Alumoxane or boron compounds such as alumoxane or MAO) are preferably used. Examples of the cocatalyst used are described in EP-0874922A2, JP-A-11-130808, JP-A-9-309925, WO00 / 20426, EP0985689A2, and JP-A-6-184179. And co-catalysts and alkylaluminum compounds. A co-catalyst such as alumoxane is used in an aluminum atom / transition metal atom ratio of 0.1 to 100,000, preferably 10 to 10,000, relative to the metal of the transition metal compound. If it is less than 0.1, the transition metal compound cannot be activated effectively, and if it exceeds 100,000, it is economically disadvantageous.

When a boron compound is used as the cocatalyst, it is used at a boron atom / transition metal atom ratio of 0.01 to 100, preferably 0.1 to 10, particularly preferably 1. If it is less than 0.01, the transition metal compound cannot be activated effectively, and if it exceeds 100, it is economically disadvantageous. The transition metal compound and the cocatalyst may be mixed and prepared outside the polymerization facility, or may be mixed in the facility during polymerization.

The aromatic vinyl compound used in the present invention includes styrene and various substituted styrenes such as p-methylstyrene, m-methylstyrene, o-methylstyrene, ot-butylstyrene, mt-butylstyrene, p- Examples include t-butyl styrene, p-chlorostyrene, o-chlorostyrene, and the like. Industrially, styrene, p-methylstyrene, p-chlorostyrene, particularly preferably styrene is used.

The aromatic polyene used in the present invention is an aromatic polyene having 10 to 30 carbon atoms and having a plurality of double bonds (vinyl group) and one or more aromatic groups and capable of coordination polymerization, One of the double bonds (vinyl group) is used for coordination polymerization, and the remaining double bond in the polymerized state is an aromatic polyene capable of anion polymerization. Preferably, any one or a mixture of two or more of orthodivinylbenzene, paradivinylbenzene and metadivinylbenzene is preferably used.

In producing the ethylene-aromatic vinyl compound-aromatic polyene copolymer in the coordination polymerization step of the present invention, the monomers, transition metal compounds and promoters exemplified above are brought into contact with each other. Any known method can be used as the method.
As the above copolymerization method, polymerization is performed in a liquid monomer without using a solvent, or pentane, hexane, heptane, cyclohexane, benzene, toluene, ethylbenzene, xylene, chloro-substituted benzene, chloro-substituted toluene, methylene chloride, chloroform. And the like, using a saturated aliphatic or aromatic hydrocarbon or halogenated hydrocarbon alone or in a mixed solvent. Preferably, a mixed alkane solvent, cyclohexane, toluene, or ethylbenzene is used. The polymerization form may be either solution polymerization or slurry polymerization. Moreover, well-known methods, such as batch polymerization, continuous polymerization, prepolymerization, and multistage polymerization, can be used as needed.
It is also possible to use a single tank or a plurality of connected tank polymerization cans or a single linear or loop polymerization apparatus or a plurality of connected pipe polymerization equipment. Pipe-shaped polymerization cans include various known mixers such as dynamic or static mixers and static mixers that also remove heat, and various known mixers such as coolers equipped with heat removal thin tubes. You may have a cooler. Moreover, you may have a batch type prepolymerization can. Furthermore, methods such as gas phase polymerization can be used.
The polymerization temperature can be in the range of 80 ° C. to 150 ° C., preferably 80 ° C. to 120 ° C., and most preferably 90 ° C. to 120 ° C.
The pressure at the time of polymerization is suitably 0.01 MPa to 10 MPa, preferably 0.1 to 3 MPa, and industrially particularly preferably 0.1 to 1 MPa.

<Anionic polymerization process>
In the anionic polymerization step of the production method of the present invention, an anionic polymerization initiator is used in the coexistence of the ethylene-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step and the anionic polymerizable vinyl compound monomer. Polymerize.
Any anionic polymerizable vinyl compound monomer can be used in the anionic polymerization step.

In particular, in the present invention, aromatic vinyl compounds such as styrene, p-methylstyrene, p-tertiary-butylstyrene, p-chlorostyrene, α-methylstyrene, vinylnaphthalene and vinylanthracene, diene compounds such as butadiene and isoprene, Acrylic acid esters such as methyl acrylate, methacrylic acid esters such as methyl methacrylate, and the like, and mixtures thereof are used. Preferably an aromatic vinyl compound or a mixture of an aromatic vinyl compound and an anionically polymerizable monomer is used, most preferably an aromatic vinyl compound, particularly styrene.
In the anionic polymerization step of the present invention, in addition to the anionic polymerizable monomer, an aromatic polyene that is not polymerized in the coordination polymerization step and remains in the polymerization solution may be polymerized.

The anionic polymerization step of the present invention is performed after the above coordination polymerization step. At this time, the copolymer obtained in the coordination polymerization step is subjected to any polymer recovery method such as a crumb forming method, a steam stripping method, a devolatilization tank, a direct desolvation method using a devolatilization extruder, etc. Then, it may be separated and purified from the polymerization solution and used in the anionic polymerization step. However, it is economically preferable that the residual ethylene is used in the next anionic polymerization step after releasing or not releasing pressure from the polymerization solution after the coordination polymerization. It is one of the features of the present invention that a polymer solution containing a polymer can be used in the cloth forming step without separating the polymer from the polymerization solution.

As the solvent for the anionic polymerization step, a mixed alkane solvent or a solvent such as cyclohexane or benzene that does not cause inconvenience such as chain transfer in the anionic polymerization is particularly preferable. If the polymerization temperature is 150 ° C. or lower, toluene, ethylbenzene, etc. Other solvents can also be used.
As the polymerization form, any known method used for anionic polymerization can be used. The polymerization temperature is suitably from -78 ° C to 200 ° C. A polymerization temperature lower than −78 ° C. is industrially disadvantageous, and if it exceeds 150 ° C., chain transfer or the like occurs, which is not suitable. Furthermore, industrially preferable, it is 0 degreeC-200 degreeC, Most preferably, it is 30 degreeC-150 degreeC.
The pressure at the time of polymerization is suitably 0.1 MPa to 10 MPa, preferably 0.1 to 3 MPa, particularly industrially particularly preferably 0.1 to 1 MPa.

In the anionic polymerization step of the present invention, a known anionic polymerization initiator can be used. Preferably, lithium salts or sodium salts such as alkyl lithium compounds, biphenyl, naphthalene, and pyrene, particularly preferably sec-butyl lithium and n (normal) -butyl lithium are used. Moreover, you may use a polyfunctional initiator, a dilithium compound, and a trilithium compound. Furthermore, you may use a well-known anionic polymerization terminal coupling agent as needed.
In the case of using methylalumoxane as a co-catalyst for the polymerization catalyst in the coordination polymerization step, the initiator is used in an amount of at least the equivalent of oxygen atoms contained therein, particularly preferably at least 2 equivalents. Is preferred. When a boron compound is used as a co-catalyst for the polymerization catalyst in the coordination polymerization step, the amount is sufficiently smaller than the oxygen atom equivalent in methylalumoxane, so the amount of initiator can be reduced. is there.

In the anionic polymerization step, the length of the cross chain and the molecular weight of the homopolymer that has not been crossed can be arbitrarily changed by appropriately adjusting the amount of the initiator.
The length (molecular weight) of the cross-chain portion can be estimated from the molecular weight of the homopolymer that has not been cross-linked, but the length is preferably 5000 to 150,000, more preferably 5000 to 100,000 as a weight average molecular weight. It is as follows. The molecular weight distribution (Mw / Mn) is preferably 3 or less, particularly preferably 1.5 or less.

Furthermore, the present invention is a method for producing a cross-copolymer, wherein the anionic polymerizable vinyl compound monomer used in the anionic polymerization step is preferably an aromatic vinyl compound monomer. Here, the aromatic vinyl compound monomer used in the coordination polymerization step and the aromatic vinyl compound monomer used in the anion polymerization step are preferably the same. Most preferably, the aromatic vinyl compound monomer used in the coordination polymerization step is styrene, and the anion polymerizable vinyl compound monomer used in the anion polymerization step is styrene, and part or all of the monomer is not yet used in the coordination polymerization step. A process for producing a cross-copolymer characterized by being reactive styrene.

The cross-copolymer of the present invention changes the mass ratio of the ethylene-aromatic vinyl compound-aromatic polyene copolymer obtained by changing the styrene (aromatic vinyl compound) unit content of the main chain or by the coordination polymerization step. The initial elastic modulus can be easily changed by changing the mass of the cross-copolymer finally obtained through the anionic polymerization step. The heat resistance (heat deformation resistance) can be maintained at about 100 ° C. (when the anionically polymerizable vinyl compound monomer is styrene). This is considered to be due to Tg (glass transition temperature) of the polystyrene block chain polymerized in the anionic polymerization step.
The cross copolymer of the present invention exhibits good moldability. The moldability can be shown by the ratio of MFR values (for example, JIS K7210) measured by changing the load at a constant temperature. For example, the ratio of the MFR values at a load of 2.16 kg and 10 kg (ratio of the MFR of the load of 10 kg to 2.16 kg: I10 / I2.16) is often in the range of 6 to 9 for ordinary polyolefins and polystyrene. On the other hand, the cross copolymer of the present invention can exhibit a value of 10 or more and about 70. This is considered to be due to the branched structure (cross structure) of the cross copolymer. When this value is low, in the case of extrusion molding, there is a case that the stress is released immediately after coming out of the mold, which is not preferable. The cross copolymer of the present invention preferably exhibits a value of 0.01 g / 10 min or more and 10 g / 10 min or less as an MFR value measured under the conditions of 200 ° C. and a load of 2.16 kg. When this MFR value is lower or higher than this, special consideration may be required during the molding process.
The cross-copolymer of the present invention can be sulfonated by a known method, for example, the method described in JP-T-2004-504928, JP-T-2004-535270, JP-T-2001-520295, or JP-T-2004-505120. The sulfonated cross-copolymer can be suitably used as a moisture permeable membrane or an ion conductive membrane.

<Resin composition>
The cross-copolymer of the present invention can be used as a composition with an aromatic vinyl compound polymer or olefin polymer described below. In this case, the present cross-copolymer can be used in the range of 1 to 99% by mass relative to the total mass of the composition. The cross copolymer of the present invention exhibits good compatibility with aromatic vinyl compound polymers and olefin polymers. Therefore, when the present cross-copolymer is used in the range of 1 to 50% by mass relative to the total mass of the composition, for example, the impact resistance of the partner aromatic vinyl compound polymer (polystyrene etc.) or polyolefin is improved or soft. When it is used in the range of 50 to 99% by mass with respect to the total mass of the composition, it is effective in adjusting the physical properties (for example, elastic modulus) of the present cross copolymer and improving the heat resistance. .

The cross copolymer of the present invention can be used as a compatibilizing agent for aromatic vinyl compound polymers and polyolefin polymers. In this case, the composition ratio of the aromatic vinyl compound polymer and the polyolefin polymer is arbitrary, and the present cross-copolymer can be used in the range of 1 to 70% by mass relative to the total mass of the composition.

Furthermore, the cross-copolymer of the present invention can be used as a composition with a block copolymer polymer, and can be used in the range of 1 to 99% by mass relative to the total mass of the composition. Since the cross-copolymer of the present invention has good softness and oil resistance, oil resistance can be imparted without impairing its softness and mechanical properties in a composition with a block copolymer polymer.

"Aromatic vinyl compound polymer"
A polymer of an aromatic vinyl compound alone or a statistical copolymer containing at least one monomer component copolymerizable with an aromatic vinyl compound and having an aromatic vinyl compound content of 10% by mass or more, preferably 30% by mass or more. Examples of the aromatic vinyl compound monomer used in the aromatic vinyl compound polymer include styrene and various substituted styrenes such as p-methylstyrene, m-methylstyrene, o-methylstyrene, ot-butylstyrene, m- Examples thereof include t-butyl styrene, p-t-butyl styrene, α-methyl styrene, etc., and compounds having a plurality of vinyl groups in one molecule such as divinylbenzene. In addition, a statistical copolymer between these plural aromatic vinyl compounds is also used. The stereoregularity between the aromatic groups of the aromatic vinyl compound may be any of atactic, isotactic, and syndiotactic.

Examples of the monomer copolymerizable with the aromatic vinyl compound include butadiene, isoprene, other conjugated dienes, acrylic acid, methacrylic acid, amide derivatives and ester derivatives thereof, acrylonitrile, maleic anhydride and derivatives thereof. The type of copolymerization is statistical copolymerization. The above aromatic vinyl compound-based polymer has a polystyrene-reduced weight average molecular weight of 30,000 or more, preferably 50,000 or more and 500,000 or less, preferably, in order to express physical properties and molding processability as a practical resin. It needs to be 300,000 or less. Further, a rubber component may be blended or grafted in order to impart impact resistance. Aromatic vinyl compound system used, for example, isotactic polystyrene (i-PS), syndiotactic polystyrene (s-PS), atactic polystyrene (a-PS), rubber reinforced polystyrene (HIPS), acrylonitrile-butadiene-styrene Polymer (ABS) resin, styrene-acrylonitrile copolymer (AS resin), styrene-methacrylic acid ester copolymer such as styrene-methyl methacrylate copolymer, styrene-diene copolymer (SBR, etc.) and water thereof Examples thereof include additives, styrene-maleic acid copolymers, styrene-imidated maleic acid copolymers, petroleum resins and hydrogenated products thereof.

"Olefin polymer"
High density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-cyclic olefin copolymer, olefin homopolymer or copolymer containing 30% by mass or more of olefin monomer units For example, isotactic polyolefin (including i-PP, homo PP, random PP, block PP), syndiotactic polyolefin (s-PP), atactic polyolefin (a-PP), olefin ethylene block copolymer , An olefin ethylene random copolymer, and an olefin butene copolymer. If necessary, a copolymer obtained by copolymerizing dienes such as butadiene and α-ω diene may be used. Examples of such include ethylene-olefin diene copolymer (EPDM), ethylene-olefin ethylidene norbornene copolymer, and the like. The above olefin polymer has a polystyrene-reduced weight average molecular weight of 10,000 or more, preferably 30,000 or more and 500,000 or less, preferably 300,000 or less, in order to develop physical properties and molding processability as practical resins. is necessary.

"Block copolymer polymer"
It is a block copolymer having a diblock, triblock, multiblock, star block or taper block structure obtained by living polymerization by anionic polymerization or other polymerization methods. Examples thereof include styrene-butadiene block copolymer (SBS), styrene-isoprene copolymer (SIS), and hydrogenated products thereof (SEBS and SIPS). The above block copolymer polymer has a polystyrene-reduced weight average molecular weight of 5,000 or more, preferably 10,000 or more and 300,000 or less, preferably 200,000 or less, in order to express physical properties and molding processability as a practical resin. is required.

The cross copolymer of the present invention can also be used as a composition with the following “other resins, elastomers, rubbers”.

"Other resins, elastomers, rubber"
Examples include petroleum resins and hydrogenated products thereof, polyamides such as nylon, polyesters such as polyimide and polyethylene terephthalate, polyvinyl alcohol, natural rubber, silicone resin, and silicone rubber.

<Plasticizer>
The cross-copolymer of the present invention can be blended with any known plasticizer conventionally used for vinyl chloride and other resins. The plasticizer preferably used is an oxygen-containing or nitrogen-containing plasticizer, and is a plasticizer selected from an ester plasticizer, an epoxy plasticizer, an ether plasticizer, or an amide plasticizer.

These plasticizers have a relatively good compatibility with the ethylene-aromatic vinyl compound-aromatic polyene copolymer used in the cross-copolymer of the present invention, are difficult to bleed, and have a low glass transition temperature. The plasticizing effect that can be evaluated by the degree to which it is applied is large and can be suitably used. When these plasticizers are used, the ethylene-aromatic vinyl compound-aromatic polyene copolymer, particularly the ethylene-aromatic vinyl compound-divinylbenzene copolymer used in the cross-copolymer of the present invention has a specific effect. It has the effect of accelerating the crystallization of isotactic alternating structure of ethylene and aromatic vinyl compound unit in the polymer and increasing the crystallinity, and also shows the effect of improving heat resistance and oil resistance in addition to the usual plasticizing effect I can do it.
On the other hand, for example, aromatic, aliphatic, and alicyclic mineral oils are easily compatible with the ethylene-aromatic vinyl compound copolymer of the present composition, and the degree to which the glass transition temperature decreases. The plasticizing effect that can be evaluated by the method is small and may not be appropriate.

Examples of ester plasticizers that can be suitably used in the present invention include various phthalic acid esters, trimellitic acid esters, adipic acid esters, sebacic acid esters, azelate esters, citrate esters, and acetyl citrate esters. Monofatty acid esters such as glutamic acid esters, succinic acid esters, and acetic acid esters, phosphoric acid esters, and polyesters thereof.

Examples of the epoxy plasticizer that can be suitably used in the present invention include epoxidized soybean oil and epoxidized linseed oil.

Examples of ether plasticizers that can be suitably used in the present invention include polyethylene glycol, polyolefin glycol, copolymers thereof, and mixtures thereof.
Examples of amide plasticizers that can be suitably used in the present invention include various sulfonic acid amides. These plasticizers may be used alone or in combination.

The ester plasticizer is particularly preferably used in the present invention. These plasticizers have the advantages of excellent compatibility with the ethylene-aromatic vinyl compound copolymer in the composition range, excellent plasticizing effect (high degree of glass transition temperature reduction), and less bled. . In addition, it has an excellent effect of promoting crystallization of an excellent ethylene-aromatic vinyl compound alternating structure, which gives a high melting point and is suitable. Furthermore, an adipate ester type or acetyl citrate ester type plasticizer is most preferably used in the present invention. When these plasticizers are used, there is an advantage that the crystallization speed is remarkably high, crystals grow in a short time from melt molding, and various physical properties are stabilized.

The compounding amount of the plasticizer is 1 part by mass or more and 30 parts by mass or less, preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the cross copolymer or the resin composition of the present invention. If the amount is less than 1 part by mass, the above effect is insufficient. If the amount is more than 30 parts by mass, it may cause bleeding, excessive softening, and excessive stickiness.

<Inorganic filler>
Hereinafter, the inorganic filler that can be used in the present invention will be described.
The inorganic filler is also used to impart flame retardancy to the present cross copolymer. The volume average particle diameter of the inorganic filler is, for example, 20 μm or less, preferably 10 μm or less. If the volume average particle diameter is less than 0.5 μm or more than 10 μm, mechanical properties (tensile strength, elongation at break, etc.) when formed into a film are reduced, and flexibility and pinholes are generated. There is. The volume average particle diameter is a volume average particle diameter measured by a laser diffraction method.

Examples of inorganic fillers include aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, triphenyl phosphite, ammonium polyphosphate, polyphosphate amide, zirconium oxide and magnesium oxide. , Zinc oxide, titanium oxide, molybdenum oxide, guanidine phosphate, hydrotalcite, snakerite, zinc borate, anhydrous zinc borate, zinc metaborate, barium metaborate, antimony oxide, antimony trioxide, antimony pentoxide, red phosphorus, Talc, alumina, silica, boehmite, bentonite, sodium silicate, calcium silicate, calcium sulfate, calcium carbonate, and magnesium carbonate, and one or more compounds selected from these are used. In particular, the use of at least one selected from the group consisting of aluminum hydroxide, magnesium hydroxide, hydrotalcite, and magnesium carbonate is excellent in flame retardancy and is economically advantageous.

The compounding quantity of an inorganic filler is 1-300 mass parts with respect to 100 mass parts of this cloth copolymer or its resin composition, Preferably it is the range of 5-200 mass parts. If the inorganic filler is less than 1 part by mass, flame retardancy may be inferior. On the other hand, when the inorganic filler exceeds 300 parts by mass, mechanical properties such as moldability and strength of the resin composition may be inferior.
When an inorganic filler is blended as a non-halogen flame retardant, char (carbonized layer) can be formed and the flame retardancy of the film can be improved.

The method for producing the resin composition, plasticizer composition, and filler composition of the present invention is not particularly limited, and a known appropriate blending method can be used. For example, melt mixing can be performed with a single-screw or twin-screw extruder, a Banbury mixer, a plast mill, a kneader, a heating roll, or the like. Prior to melt mixing, the raw materials may be mixed uniformly with a Henschel mixer, ribbon blender, super mixer, tumbler, or the like. The melt mixing temperature is not particularly limited, but is generally 100 to 300 ° C, preferably 150 to 250 ° C.

As a molding method for obtaining a molded body of the cross copolymer of the present invention or various compositions thereof, vacuum molding, injection molding, blow molding, inflation molding, extrusion molding, profile extrusion molding, roll molding, A known molding method such as calendar molding can be used, whereby various sheets, films, bags, tubes, containers, foamed materials, foamed sheets, wire covering materials, etc. can be formed.
Furthermore, since the resin and the resin composition described in the present invention basically do not contain halogen, they have a basic feature that environmental adaptability and safety are high.

<Film, sheet>
When the cross copolymer of the present invention or the resin composition thereof is used as a film, the thickness thereof is not particularly limited, but is generally 3 μm to 1 mm, preferably 10 μm to 0.5 mm.
In order to produce a film or sheet comprising the resin composition of the present invention, a molding method such as inflation molding, T-die molding, calendar molding or roll molding can be employed. For the purpose of improving physical properties, the film of the present invention may be other suitable films such as isotactic or syndiotactic polypropylene, high density polyethylene, low density polyethylene (LDPE or LLDPE), polystyrene, polyethylene terephthalate, It can be multilayered with a film such as ethylene-vinyl acetate copolymer (EVA). Furthermore, the film of this invention can have self-adhesiveness and adhesiveness by selecting a composition suitably. However, when stronger self-adhesiveness is required, a multilayer film with another film having self-adhesiveness can be formed.

Although the specific use of the film of this invention is not specifically limited, It is useful as a general packaging material and a container, and can be used for a packaging film, a stretch film, a shrink film, a bag, a pouch, a dicing film for electronic materials, and the like. it can. In particular, a film comprising the copolymer film of the present invention or a resin composition film comprising the copolymer, or a film comprising such a film as its film structure has a low elastic modulus and anisotropy in elongation, so that it is an electronic material. Useful as a dicing film.
<Tape substrate>
Moreover, the film which consists of a resin composition which mainly contains the cross copolymer of this invention or a cross copolymer can be used as various tape base materials. Here, the resin composition mainly containing the cross-copolymer is contained in an amount of 50% by mass or more based on the tape base material mass (mainly the resin mass) excluding the above <inorganic filler>. It shows that. Other resins that may be blended as the resin composition are arbitrary, but are preferably the above “aromatic vinyl compound polymer”, “olefin polymer”, and / or “block copolymer polymer”. . These are appropriately blended for adjusting the elastic modulus and modulus of the tape substrate and imparting heat resistance.
The above <inorganic filler> is suitably added to impart flame retardancy to the tape substrate, and its blending amount is arbitrary within a known range, but generally with respect to the total weight of the tape substrate. 1 mass% or more and 70 mass% or less.
When used as a tape base material, the softness, oil resistance, and characteristic tensile properties of the present cross copolymer are advantageous. In order to form an adhesive tape using a composition containing the present cross copolymer as a tape substrate, a known pressure-sensitive adhesive, an additive, and a known molding method are used. Such pressure-sensitive adhesives, additives, and molding methods are described in, for example, Japanese Patent Publication No. 2000-111646. Adhesive tapes comprising this tape base material are various binding tapes, sealing tapes, protective tapes, fixing tapes, various tapes for electronic materials, such as dicing. It can be suitably used as a tape substrate such as a tape for tape, a tape for back grinding, or a tape for masking. Also useful as various labels

If necessary, the film of the present invention can be subjected to surface treatment such as corona, ozone, and plasma, application of an antifogging agent, application of a lubricant, printing, and the like. The film of the present invention can be produced as a stretched film subjected to stretching orientation such as uniaxial or biaxial as required. If necessary, the films of the present invention can be bonded to each other or to other materials such as thermoplastic resins by a technique such as fusion using a technique such as heat, ultrasonic waves or high frequency, adhesion using a solvent or the like.

Furthermore, when the film of the present invention has a thickness of, for example, 100 μm or more, a tray for packaging foods, electrical products and the like can be formed by a technique such as vacuum forming, compression forming, thermoforming such as pressure forming.

The tape base material can be blended with known colorants, antioxidants, ultraviolet absorbers, lubricants, stabilizers, and other additives as long as they do not inhibit the effects of the present invention. .

In the present invention, the tape substrate is usually blended as necessary with an ethylene-aromatic vinyl compound-aromatic polyene copolymer, an aromatic vinyl compound resin, an olefin resin, and an inorganic filler (and a filler, etc.). Material) is dry blended, the mixture is kneaded using a Banbury mixer, roll, extruder, etc., and the kneaded product is formed into a film by a known molding method such as compression molding, calendar molding, injection molding, extrusion molding, or the like. Obtained by molding.

Although the thickness of a tape base material changes also with uses of an adhesive tape, it does not restrict | limit in particular, For example, 40-500 micrometers, Preferably it is 70-200 micrometers, More preferably, it is 80-160 micrometers. The tape substrate may have a single layer form or may have a multiple layer form.

By irradiating the tape base material with an electron beam for crosslinking, the tape base material can be prevented from being deformed or contracted when placed under a high temperature, and the temperature dependence can be reduced. In this case, the irradiation amount of the electron beam is preferably in the range of 10 to 150 Mrad (mega rad). The range of 15 to 25 Mrad is preferable. If the irradiation amount is less than 10 Mrad, the temperature dependency is not improved. On the other hand, if the irradiation amount exceeds 150 Mrad, the tape base material is deteriorated by the electron beam, which may cause a problem in workability in post-processing. A cross-linking agent for promoting electron beam cross-linking may be added. Specific examples of the crosslinking agent include low molecular weight compounds and oligomers having at least two carbon-carbon double bonds in the molecule, such as acrylate compounds, urethane acrylate oligomers, and epoxy acrylate oligomers.

The pressure-sensitive adhesive tape of the present invention is configured by providing a pressure-sensitive adhesive layer on at least one surface of the tape base material. As the pressure-sensitive adhesive, all existing pressure-sensitive adhesives such as rubber-based, hot-melt-based, acrylic-based, and emulsion-based can be applied. Moreover, in order to make these adhesives have desirable performance, tackifiers, anti-aging agents, curing agents and the like can be blended.

As the base polymer of the rubber adhesive, natural rubber, recycled rubber, silicone rubber, isoprene rubber, styrene butadiene rubber, polyisoprene, NBR, styrene-isoprene copolymer, styrene-isoprene-butadiene copolymer and the like are preferable. A crosslinking agent, a softening agent, a filler, a flame retardant, etc. can be added to a rubber-type adhesive as needed. Specific examples include isocyanate crosslinking agents as crosslinking agents, liquid rubber as softening agents, calcium carbonate as fillers, and inorganic flame retardants such as magnesium hydroxide and red phosphorus as flame retardants.

Examples of the acrylic pressure-sensitive adhesive include a homopolymer of (meth) acrylic acid ester or a copolymer with a copolymerizable monomer. (Meth) acrylic acid ester or copolymerizable monomer includes (meth) acrylic acid alkyl ester (for example, methyl ester, ethyl ester, butyl ester, 2-ethylhexyl ester, octyl ester, etc.), (meth) acrylic acid glycidyl ester , (Meth) acrylic acid, itaconic acid, maleic anhydride, (meth) acrylic acid amide, (meth) acrylic acid N-hydroxyamide, (meth) acrylic acid alkylaminoalkyl ester (for example, dimethylaminoethyl methacrylate, t- Butylaminoethyl methacrylate), vinyl acetate, styrene, acrylonitrile and the like. Of these, as the main monomer, an alkyl acrylate ester whose homopolymer (homopolymer) usually has a glass transition temperature of −50 ° C. or lower is preferred.

The tackifying resin agent can be selected in consideration of the softening point, compatibility with each component, and the like. Examples include terpene resins, rosin resins, hydrogenated rosin resins, coumarone / indene resins, styrene resins, aliphatic and alicyclic petroleum resins and their hydrogenated products, terpene-phenol resins, xylene resins. And other aliphatic hydrocarbon resins or aromatic hydrocarbon resins. The softening point of the tackifying resin is preferably 65 to 170 ° C, and moreover, an alicyclic saturated hydrocarbon resin of a petroleum resin having a softening point of 65 to 130 ° C, a polyterpene resin having a softening point of 80 to 130 ° C, and a softening point of 80 to 130. More preferred is a glycerin ester of hydrogenated rosin at 0 ° C. These can be used either alone or in combination.

The anti-aging agent is used to improve the rubber-based pressure-sensitive adhesive because it has an unsaturated double bond in the rubber molecule and is likely to deteriorate in the presence of oxygen or light. Examples of the anti-aging agent include phenolic anti-aging agents, amine-based anti-aging agents, benzimidazole-based anti-aging agents, dithiocarbamate-based anti-aging agents, phosphorus-based anti-aging agents and the like alone or as a mixture. it can.

Examples of the curing agent for the acrylic pressure-sensitive adhesive include isocyanate-based, epoxy-based, and amine-based curing agents, and these may be used alone or as a mixture. Specific examples of the isocyanate curing agent include polyvalent isocyanate compounds such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylene diisocyanate, and diphenylmethane. -4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, Lysine isocyanate and the like.

The means for applying to the tape substrate such as the pressure-sensitive adhesive, pressure-sensitive adhesive imparting agent and anti-aging agent constituting the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape is not particularly limited. For example, pressure-sensitive adhesive, pressure-sensitive adhesive application There is a method in which a pressure-sensitive adhesive solution comprising an agent and an anti-aging agent is applied to one side of the tape substrate by a transfer method and dried.

Although the thickness (thickness after drying) of an adhesive layer can be suitably selected in the range which does not impair adhesiveness and handleability, although the thickness of an adhesive layer changes with uses of an adhesive tape, it is 5-100 micrometers, Preferably 10-50 μm. If it is thinner than this, the adhesive force and the unwinding force may decrease. On the other hand, if it is thicker than this, the coating performance may deteriorate.
It is preferable that the tape substrate of the adhesive tape, the binding tape, and the sealing tape satisfy the following conditions. The cross-copolymer of the present invention can satisfy the following conditions when taped by the above method, and is suitable as a tape substrate for adhesive tape, binding tape, and sealing tape. Can be used.
As conditions for the tape substrate,
(1) “Surface condition” is a clean and smooth surface,
(2) The initial elastic modulus (MPa) at room temperature in the MD direction is 50 MPa or more and less than 700 MPa,
(3) Tensile elongation at break in the MD direction is 100% to less than 500%,
(4) The breaking strength in the MD direction (MPa) is 10 MPa or more and less than 70 MPa,
(5) 10% modulus in MD direction (tensile stress at 10% elongation) is 2 MPa or more and less than 15 MPa,
(6) The modulus ratio in the MD direction (100% modulus / 10% modulus) is 1.6 or more and less than 5,
(7) “Heat shrinkage”, that is, an evaluation test chamber set at a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5% RH after leaving a 100 mm square tape base for 10 minutes in an atmosphere of 110 ° C. The shrinkage in the MD direction is less than 10%
(8) “Hand cutting”, that is, when the tape is cut by hand, the cut edge slightly grows, but it cuts cleanly.
(9) “Blocking property”, that is, the tape base material is cut into a shape of 50 mm × 100 mm, two pieces of 50 mm × 50 mm are stacked and left at 50 ° C. for 24 hours under a load of 15 kg, and then the tape Even if the substrate is peeled off or attached, it can be easily peeled off.
The MD direction indicates the longitudinal direction of the tape.

<Dynamic vulcanizate>
The cross-copolymer of the present invention can be made into a thermoplastic elastomer composition by dynamic addition treatment together with other polymers. Specifically, the cross-copolymer of the present invention is 50% by mass to 95% by mass, preferably 60% by mass to 95% by mass, and the other polymer is 5% by mass to 50% by mass, preferably 5% by mass. % Is a thermoplastic elastomer obtained by dynamic vulcanization treatment. Here, the other polymer is the “aromatic vinyl compound polymer”, “olefin polymer”, “block copolymer polymer”, or “other resin, elastomer, rubber”. .
More preferably, the thermoplastic elastomer obtained by dynamic vulcanization treatment containing 50% by mass to 95% by mass of the cross-copolymer of the present invention and 5% by mass to 50% by mass of a crystalline propylene polymer. -A composition. Here, the crystalline propylene-based polymer is a polypropylene-based polymer having isotactic or syndiotactic stereoregularity among the above-mentioned olefin polymers, and has a crystal melting point of 100 ° C. or higher and 170 ° C. or lower, preferably Is a polymer having a temperature of 120 ° C to 170 ° C. The crystalline propylene polymer can be used alone or in combination.
The thermoplastic elastomer composition of the present invention comprises (A) a blend comprising the cross-copolymer of the present invention and (B) other polymer (such as a crystalline propylene polymer), an organic peroxide or a phenol resin. It can be obtained by dynamic vulcanization treatment (dynamic heat treatment) in the presence of a crosslinking agent. The dynamic vulcanization treatment is a technique in which dispersion and crosslinking are simultaneously caused by strongly kneading various compounds in a molten state under conditions where the crosslinking agent reacts. Y. It is described in detail in Coran et al. (Rub. Chem. And Technol. Vol. 53, 141 (1980)) and is widely known. The dynamic vulcanization is performed using a Banbury mixer, a closed kneader such as a pressure kneader, a single or twin screw extruder, and the like. The kneading temperature is usually 130 to 300 ° C, preferably 150 to 250 ° C. The kneading time is usually 1 to 30 minutes.
Specific examples of the organic peroxide used in the dynamic vulcanization treatment include dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) -hexane, and 2,5-dimethyl. -2,5-di (tert-butylperoxy) -hexyne-3, di-tert-butyl peroxide and the like. In the present invention, the organic peroxide is preferably used in a proportion of 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the (A) cross-copolymer of the present invention. In addition, during the dynamic vulcanization treatment with organic peroxides, it is possible to add a peroxide crosslinking aid such as a maleimide compound and a polyfunctional vinyl monomer such as divinylbenzene or trimethylolpropane trimethacrylate. .
In addition to the polymer component, the “plasticizer” and “inorganic filler” can be added during the dynamic vulcanization treatment. “Plasticizer” is preferably used in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the polymer component, and “inorganic filler” is preferably used in an amount of 1 to 200 parts by mass with respect to 100 parts by mass of the polymer component.

<Composition with petroleum resin / hydrogenated petroleum resin>
A petroleum resin and / or hydrogenated petroleum resin can be added to the cross copolymer of the present invention to obtain a resin composition. The blending is as described above, preferably 70 mass% or more and 99 mass% or less of the cross-copolymer of the present invention, petroleum resin and / or hydrogenated petroleum resin in the range of 1 mass% or more and 30 mass% or less, Particularly preferably, the cross copolymer of the present invention is in the range of 80% by mass to 99% by mass and the hydrogenated petroleum resin is in the range of 1% by mass to 20% by mass.
In the case of the above blending range, the moldability (specified by the MFR value) can be widely controlled without impairing the original mechanical properties of the cross copolymer, and can be adjusted to the MFR suitable for the molding method. The MFR of the resin composition increases as the blending amount of the petroleum resin and / or hydrogenated petroleum resin having a molecular weight sufficiently lower than that of the cross-copolymer increases. The MFR can be easily adjusted by those skilled in the art by adjusting the blending amount within the above range.
Furthermore, blending petroleum resin and / or hydrogenated petroleum resin within this range has the effect of significantly improving the transparency of the cross-copolymer. In consideration of coloring and transparency of the resin composition, a hydrogenated petroleum resin having high colorless transparency is preferable for this purpose. When the amount of petroleum resin and / or hydrogenated petroleum resin is less than this range, the above effect is not sufficient. When the amount is large, the resin composition tends to exhibit adhesiveness derived from petroleum resin and / or hydrogenated petroleum resin. Some are not preferred. Of course, in the case where the adhesiveness is required, for example, in the case of an adhesive, a heat seal film or the like, it can be blended more than the above range.

<Composition with antiblocking agent / slip agent>
An antiblocking agent and / or a slip agent can be added to the cross copolymer of the present invention to obtain a resin composition. The blending differs depending on the material, so it cannot be said uniformly. However, the cross-copolymer of the present invention is preferably 99.9% by mass to 99% by mass, and the anti-blocking agent is 0.01% by mass to 1%. It is the range of the mass% or less.
In the case of the above blending range, the effects as a molding aid such as blocking prevention, processability, mold releasability improvement and surface modification are exhibited without impairing the original mechanical properties of the cross-copolymer. Known anti-blocking agents and slip agents are used, but as such additives, saturated fatty acid or unsaturated fatty acid amides such as stearic acid amide, oleic acid amide, erucic acid amide, palmitic acid amide, behenine Use of acid amide, oleyl palmitoamide, stearyl erucamide, N, N′-methylenebisstearylamide, N, N′-ethylenebiserucamide, hydrogenated castor oil, silica or the like I can do it.

<Composition with block copolymer>
Since the cross-copolymer of the present invention is particularly excellent in its softness, it can be made into the above-mentioned block copolymer, particularly a hydrogenated block copolymer and a composition, thereby maintaining oil resistance while maintaining softness and mechanical properties. It is possible to impart mechanical properties similar to PVC. Crystalline polypropylene (such as isotactic or syndiotactic polypropylene) may be blended in the composition in order to further impart heat resistance.

<Foam>
Moreover, the cross copolymer of this invention can be used conveniently as a foam (foam material). A known manufacturing method can be used as the method for manufacturing the foam. Although there is no restriction | limiting in particular in the manufacturing method of a foam, Well-known techniques, such as the method of adding foaming agents, such as an inorganic type and an organic type chemical foaming agent, a physical foaming agent, can be illustrated. In general, the cross-copolymer of the present invention and a blowing agent, and if necessary, a crosslinking agent and other additives are heated and melted and heated and compressed while extruding, and then the pressure is reduced and foamed. Form it. The foaming agent and, if necessary, the radical crosslinking agent may be added before or after the polymer is dry blended or heated and melted. These heat blends can be carried out by a known method such as an extruder, a mixer, or a blender. In addition to the above-described method of adding a cross-linking agent, there is a method of using a radiation (electron beam, gamma ray, etc.). Known techniques relating to foams are described in, for example, “Plastic Foam Handbook” (published by Nikkan Kogyo Shimbun, 1973).
In addition, the methods described in WO 00/37517 and JP-T-2001-514275 can be preferably used for producing a foam. The cross-copolymer of the present invention has a characteristic that the crystallinity is not more than a certain value, and therefore a foam having excellent softness and texture can be easily obtained. In producing the foam of the present invention, the composition of the above “aromatic vinyl compound polymer”, “olefin polymer”, “block copolymer polymer” and the cross copolymer of the present invention is used. It may be used.
If necessary, a dispersant, a softener, an anti-tacking agent, a filler, a pigment, and the like can be added to the foam of the present invention.
There is no restriction | limiting in particular in the method to manufacture the foam of this invention, The physical foaming method by gas injection | pouring, the foaming method by water, the chemical foaming method by a chemical foaming agent, etc. can be illustrated. It is also possible to add a foaming agent to the beads or the like and foam them later.
There are no particular limitations on the molding method of the obtained foam sheet, film, etc., such as extrusion molding, injection molding, blow molding, etc. Furthermore, the sheet film etc. can be molded into a container etc. by thermoforming, compression molding, etc. is there. Moreover, embossing, printing, etc. can also be performed. This cross copolymer is characterized by having excellent printability.
The foam of the present invention can be used as a container for building materials such as floor materials, wall materials and wallpaper, interior / exterior products for automobiles, electrical material parts, gaskets, cushioning materials, foods and the like.
The composition, cross-linked product, and foam containing the cross-copolymer of the present invention are useful as a film, a sheet, a tube, a container and the like. In particular, it can be suitably used as building materials, wall materials, wallpaper, and floor materials. Such building materials, wall materials, wallpaper, and floor materials are described in, for example, WO96 / 04419, EP0661345, WO98 / 10160, and the like. When used in these applications, the high mechanical strength and the ability to fill the filler with a high content while maintaining the mechanical properties and physical properties such as elongation indicate that flame retardancy can be imparted particularly when used in these applications. Meaning and value.

<Wire covering material>
The cross-copolymer and resin composition described in the present invention can be suitably used as various electric wires and cable coating materials. In particular, a composition with a filler and / or a known flame retardant is excellent in softness, mechanical properties, and oil resistance, and is suitable for such applications. Moreover, in order to improve heat resistance, it is also possible to perform various well-known crosslinking methods, for example, the chemical crosslinking by a crosslinking agent, the crosslinking method by an electron beam, etc.

EXAMPLES Hereinafter, although an Example demonstrates this invention, these Examples do not limit this invention.

  The analysis of the copolymer obtained in the examples was carried out by the following means.

The styrene content in the copolymer was determined by ¹ H-NMR, and α-500 manufactured by JEOL Ltd. was used as the instrument. It was dissolved in deuterated 1,1,2,2-tetrachloroethane and the measurement was performed at 130 ° C. The area intensity of the peak derived from the phenyl group proton (6.5 to 7.5 ppm) and the proton peak derived from the alkyl group (0.8 to 3 ppm) was compared based on TMS.

As for the molecular weight, the weight average molecular weight and the number average molecular weight in terms of standard polystyrene were determined using GPC (gel permeation chromatography). High-temperature GPC measurement uses HLC-8121GPC / HT manufactured by Tosoh Corporation, and the column uses TSKgelGMHHR-HHT (manufactured by Tosoh Corporation) and orthodichlorobenzene as a solvent, and a flow rate of 1.0 ml / min. Measured at 145 ° C. In addition, the L-5030 column manufactured by Hitachi, Ltd. was connected in series with two TSK-GEL MultiporeHXL-M (manufactured by Tosoh Corporation), and the flow rate was 1.0 ml / min. , Measured at 40 ° C.

DSC measurement was performed under a nitrogen stream using a DSC200 manufactured by Seiko Instruments Inc. That is, using 10 mg of the resin composition, DSC measurement was performed from −50 ° C. to 180 ° C. at a temperature rising rate of 10 ° C./min, and the melting point, heat of crystal melting, and glass transition point were determined. After the first measurement, the second measurement performed after quenching with liquid nitrogen was not performed.

As a sample for evaluating physical properties, a sheet having a thickness of 1.0 mm formed by a hot press method (temperature 200 ° C., time 5 minutes, pressure 100 kg / cm 2) was used.

<Tensile test>
In accordance with JIS K-6251, the sheet was cut into a No. 2 1/2 type test piece shape, and measured using a Shimadzu AGS-100D type tensile tester at a tensile speed of 300 mm / min.

<Total light transmittance, haze>
Transparency is a turbidimeter manufactured by Nippon Denshoku Industries Co., Ltd. according to the method for testing optical properties of JIS K-7105 plastic after forming a sheet with a thickness of 1 mm by the hot press method (temperature 200 ° C., time 5 minutes, pressure 100 kg / cm 2 G). Total light transmittance and haze were measured using NDH2000.

<Divinylbenzene>
The divinylbenzene used in Examples and Comparative Examples 1, 2, 4, and 5 was manufactured by Aldrich Corporation (purity 80% as divinylbenzene, meta isomer, para isomer mixture, meta isomer: para isomer mass ratio 70:30. Therefore, the isomer purity of metadivinylbenzene is 70% by mass).
The metadivinylbenzene used in Comparative Example 3 is metadivinylbenzene (isomer purity 97% or more) manufactured by Asahi Kasei Finechem. The isomer purity in this case is a ratio of metadivinylbenzene to various divinylbenzene isomers of ortho, meta, and para.

<Gel content>
The gel content of the cross-copolymer was measured according to ASTM D-2765-84. That is, a precisely weighed 1.0 g polymer (a molded product having a diameter of about 1 mm and a length of about 3 mm) was wrapped in a 100 mesh stainless steel net bag and precisely weighed. After extracting this in boiling xylene for about 5 hours, the net bag was collected and dried in a vacuum at 90 ° C. for 10 hours or more. After cooling sufficiently, the net bag was precisely weighed, and the polymer gel amount was calculated by the following formula.
Gel amount = mass of polymer remaining in mesh bag / initial polymer mass × 100

<Catalyst (transition metal compound)>
In the following Examples and Comparative Examples, rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride (Chemical Formula 6) was used as a catalyst (transition metal compound).

Example 1
<Synthesis of cross copolymer>
Using rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride as a catalyst, the reaction was carried out as follows.
Polymerization was carried out using an autoclave with a capacity of 10 L, a stirrer and a heating / cooling jacket.
Charge 4400 ml of cyclohexane, 400 ml of styrene, and divinylbenzene (14 mmol as meta + para total of divinylbenzene) and bubbling about 100 L of dry nitrogen at an internal temperature of 60 ° C. to purge the system with nitrogen. The water in the reaction solution was removed. 12.6 mmol of triisobutylaluminum 8.4 mmol and methylalumoxane (manufactured by Tosoh Finechem Co., Ltd., MMAO-3A) were added based on Al, and the mixture was heated and stirred at an internal temperature of 100 ° C. Immediately after introduction of ethylene and stabilization at a pressure of 0.5 MPa (5.1 Kg / cm ² ), rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride was removed from a catalyst tank placed on the autoclave. About 30 ml of a toluene solution in which 40 μmol and 0.98 mmol of triisobutylaluminum were dissolved was added to the reaction solution. While maintaining the internal temperature at 100 ° C. and the pressure at 0.5 MPa, polymerization was carried out for 1 hour (coordination polymerization step). The ethylene consumption at this stage was about 250 L under standard conditions. A small amount (several tens of ml) of the polymerization solution was sampled, and a polymer was precipitated with methanol to obtain a sample for the coordination polymerization step. From this sampling solution, the polymer yield in the coordination polymerization step, the composition, the conversion rate of styrene, divinylbenzene and the like were determined by gas chromatography.
The supply of ethylene to the polymerization can was stopped and ethylene was released. 26 mmol of sec-butyllithium was introduced from the catalyst tank into the polymerization can with nitrogen gas. Anion polymerization started immediately, and the internal temperature rose from 60 ° C to 80 ° C. The temperature was maintained at 60 to 70 ° C. for 30 minutes as it was, and stirring was continued to continue polymerization (anionic polymerization step).
After the completion of the polymerization, the obtained polymerization solution was poured little by little into a large amount of vigorously stirred methanol solution to recover the polymer. The polymer was air-dried at room temperature for 1 day and then dried at 50 ° C. in a vacuum until no mass change was observed. 675 g of polymer (cross copolymer) was obtained.

In Examples 2 to 10, polymerization was performed in the same procedure as in Example 1 under the conditions described in Table 1.

In Examples 11 to 15, polymerization was carried out using an autoclave with a capacity of 50 L, a stirrer and a heating and cooling jacket, the polymerization temperature in the coordination polymerization step was set to 90 to 95 ° C., and the same procedure as in Example 1 was used. Polymerization was carried out under the conditions described. The polymer was treated and recovered by the crumb forming method as follows. The polymerization solution was put in 40 L of 92 ° C. heated water containing a vigorously stirred dispersant (Pluronic P-103: trade name) over 0.5 hours. After stirring at 98 ° C. for 0.5 hour, hot water containing crumb was poured into cold water, and crumb was recovered. The crumb was air-dried at room temperature all day and night, and then vacuum-dried at 50 ° C. to obtain a polymer having a good crumb shape with a size of several millimeters.

Comparative Example 1 (same as WO00 / 037517 Example 1)
The polymerization was carried out at a polymerization temperature of 70 ° C. in the coordination polymerization step. Outside the specified temperature range of the present invention, the resulting copolymer was opaque.

Comparative example 2 (same as WO00 / 037517 example 4)
Polymerization was performed under substantially the same conditions as in Comparative Example 1 except that toluene was used as the polymerization solvent and the polymerization temperature in the coordination polymerization step was 50 ° C. Outside the specified temperature range of the present invention, the resulting copolymer was opaque.

Comparative Example 3
A cross copolymer was synthesized in which the composition of the ethylene-styrene-divinylbenzene copolymer obtained in the coordination polymerization step was outside the composition range of the cross copolymer of the present invention with a styrene unit content of 4 mol%. The styrene unit content of the present invention was out of range and the resulting copolymer was opaque.

Comparative Example 4
Synthesis of a cross copolymer in which the composition of the ethylene-styrene-divinylbenzene copolymer obtained in the coordination polymerization step is less than 0.01 mol% of the divinylbenzene unit content and out of the composition range of the cross copolymer of the present invention. did. The divinylbenzene unit content of the present invention was out of range and the resulting copolymer was opaque.

Comparative Example 5
Polymerization is carried out using an autoclave with a capacity of 50 L, a stirrer and a heating / cooling jacket, the polymerization temperature in the coordination polymerization step is 85 ° C., and polymerization is carried out under the conditions described in Table 1 in the same procedure as in Example 13. The obtained polymerization solution was poured little by little into a large amount of vigorously stirred methanol solution to recover the polymer. The composition of the ethylene-styrene-divinylbenzene copolymer obtained in the coordination polymerization step was 3.7 kg of polymer having a styrene unit content of 31 mol% and out of the composition range of the cross copolymer of the present invention.

Tables 2 and 3 show the analysis results of the polymers obtained in the examples and comparative examples.
The analytical value of the polymer obtained in the coordination polymerization step is determined by precipitating a small amount (several tens ml) of the polymer sampled at the end of the coordination polymerization step in methanol, collecting the polymer, and analyzing it. The polymer yield, composition, molecular weight, conversion rate, etc. in the coordination polymerization step were determined. The divinylbenzene content of the polymer obtained in the coordination polymerization step is calculated from the corresponding peak area in 1H-NMR measurement and the amount of unreacted divinylbenzene in the polymerization solution obtained by gas chromatography analysis and used for polymerization. It was determined from the difference in the amount of divinylbenzene.
Further, in the table, the TUS / DOU value of the main chain ethylene-styrene-divinylbenzene copolymer obtained in the coordination polymerization step of this example is shown in accordance with US Pat. No. 6,096,849. Here, TUS is the total vinyl group content of the copolymer, and is the sum of the vinyl group content derived from the aromatic polyene (divinylbenzene) unit and the polymer terminal vinyl group content. Obtained by NMR measurement. The DOU value is the divinylbenzene unit content contained in the main chain ethylene-styrene-divinylbenzene copolymer.
In the ethylene-aromatic vinyl compound-aromatic polyene copolymer (ethylene-styrene-divinylbenzene copolymer) obtained in the coordination polymerization step of the present invention, the TUS / DOU value is higher than 1.1. The value generally ranges from 1.2 to 10 and preferably from 1.2 to 3. When the TUS / DOU value is larger, the aromatic polyene unit content is too small, and the function as the cross copolymer of the present invention may be lost. In addition, when the TUS / DOU value is 1.1 or less, the aromatic polyene unit content is too much and the function derived from the main chain is easily lost, and the molding processability of the cross copolymer may be deteriorated. There is a risk that a gel component is generated in the cross-copolymer.

Table 4 shows the measurement results of transparency, mechanical properties, MFR, and gel content obtained in each Example and Comparative Example.

The ethylene-styrene-divinylbenzene copolymer obtained in the coordination polymerization step of this example has a styrene unit content of 6.4 mol% to less than 15 mol%, and a divinylbenzene unit content of 0.02 mol% to 0.09. Crystal by DSC of ethylene-styrene-divinylbenzene copolymer obtained in the coordination polymerization step of this example and the cross-copolymer finally obtained through the anionic polymerization step, having a composition of less than mol% All the heats of fusion showed the value of 80 J / g or less.

The mass ratio of the polymer obtained in the coordination polymerization step of this example was 57% by mass or more and 94% by mass or less based on the mass of the cross-copolymer finally obtained through the anionic polymerization step. The obtained cross copolymer had an initial elastic modulus of 15 to 150 MPa.
In the coordination polymerization step, when the polymerization temperature is 80 ° C. or higher and 150 ° C. or lower, the obtained cross-copolymer is transparent, the haze of the sheet having a thickness of 1 mm is 30% or less, and the total light transmittance. Indicates a value of 75% or more.

All the cross-copolymers obtained in this example all exhibited an elongation of 300% or more and a breaking strength of 10 MPa or more, and had sufficient mechanical properties and transparency as a thermoplastic elastomer. On the other hand, as in Comparative Examples 1 and 2, when the divinylbenzene content is low or the polymerization temperature in the coordination polymerization step is less than 80 ° C., it is opaque.
In the examples of WO 00/37517, a cross-copolymer obtained under the condition of coordination polymerization process temperature of 50 to 70 ° C. is described, and its haze was 35% at best.
A TEM photograph of the polymer (cross copolymer) obtained in Example 1 is shown in FIG. The cross-copolymer has a relatively uniform nanoscale phase separation structure of about 30 to 50 nm, which is a relatively uniform polymer having a block chain composed of different kinds of polymers, That is, it indicates the presence of a cross copolymer.

Moreover, as shown in Comparative Example 3, when the styrene unit content of the ethylene-styrene-divinylbenzene copolymer obtained in the coordination polymerization step is less than 5 mol%, the degree of crystallinity becomes high and further transparent. Sex may be lost.

According to JIS C3005, a heat deformation test was performed to determine the thickness reduction rate.
A test piece of 30 mm × 15 mm × 2 mm was cut out from a sheet obtained by press molding (200 ° C., 100 kg / cm 2) and used for the test. After heating at 75 ° C. for 30 minutes, the sample piece was subjected to a load of 1.5 kg at 75 ° C., and the thickness of the sample piece after 30 minutes was measured to determine the thickness reduction rate before and after heating.
Example 3 Thickness reduction rate 7.4%
Example 11 Thickness reduction rate 1.5%
Comparative Example 5 Thickness reduction rate 25.0%
The cross-copolymer of the present invention has better thermal stress deformability (measurement temperature, lower thickness reduction rate under lower conditions) than a cross-copolymer (Comparative Example 5) having a different main chain composition. You can see that

<Taber abrasion test>
As a sheet-like molded body having a thickness of 2 mm, an amount of Taber abrasion when measured under conditions of 1 kg load and 1000 revolutions using an H-22 wear wheel according to JIS K-6264 was measured. Summarized in In Table 5, polyvinyl chloride (PVC) and styrene-based hydrogenated resin (SEBS) are also listed for comparison. It can be seen that the copolymer obtained by this production method is excellent in wearability with an abrasion amount of 100 mg or less.
<Rubbing wear test>
As a sheet-like molded body having a thickness of 1 mm, a reciprocating vibration test was performed 10,000 times with a 500 g load cotton cloth (gold width 3). It can be seen that the copolymer obtained by this production method has a small amount of wear and excellent wear properties.
Example 5 Abrasion amount 11 mg
Example 11 Abrasion amount 90 mg

<Film, tape substrate>
In order to evaluate the cross-copolymer of the present invention as a film machine substrate or a tape substrate, film production and physical property evaluation were performed using a two-roll roll and a calendar molding machine.

Trial production of a film using a two-roll molding machine was performed using a test mixing roll (NS-155 type) manufactured by Nishimura Machinery. The roll temperature was appropriately adjusted in the range of 120 ° C. to 170 ° C. for each polymer sample. In the two-roll molding, additives were blended in the following proportions with respect to 100% by mass of each polymer or resin composition.
Phosphate ester (manufactured by Sakai Chemical Industry Co., Ltd.) H-933D-3 (lubricant), 0.5% by mass
Zinc stearate (manufactured by Sakai Chemical Industry Co., Ltd.) LTB-1830 (lubricant), 0.3% by mass
Erucamide (made by Kao Corporation) (anti-blocking agent), 1.0% by mass

In the trial production of a film by calendar, the following lubricant and antiblocking agent were blended with 100 mass% of the blended resin of Example 13 and Comparative Example 5 in the table, and kneaded with a Banbury mixer.
Phosphate ester (manufactured by Sakai Chemical Industry Co., Ltd.) H-933D-3 (lubricant), 0.5% by mass
Zinc stearate (manufactured by Sakai Chemical Industry Co., Ltd.) LTB-1830 (lubricant), 0.3% by mass
Cross-linked beads (manufactured by Sekisui Plastics Co., Ltd.) SBX-8 (anti-blocking agent) 0.3% by mass

Thereafter, a film having a thickness of about 100 μm was prepared and evaluated by calendering (roll temperature: 165 ° C.).

Table 6 shows the measurement results of the return rate of a film having a thickness of about 100 μm obtained by calendering using Example 13 and Comparative Example 5. The return rate was evaluated based on the return of elongation after 180 seconds had elapsed after releasing the stress after fixing the sample for 10 minutes with the sample stretched 50%.

Return rate (%) = (Elongation at 50% −Residual elongation after 180 seconds after stress release) / Elongation at 50% × 100

That is, a high return rate means excellent elasticity recovery, and a low return rate means that recovery of elastic modulus is slow.
It can be said that the cross copolymer of the present invention is excellent in elastic recovery even when compared with the sample outside the composition range of the present invention in Comparative Example 5.

In Table 7, the elastic modulus in MD direction and TD direction of the film of about 100 μm thickness obtained with the two rolls using Examples 2 and 13 and Comparative Example 3 was measured, and the MD / The measurement result of TD elastic modulus ratio was shown. The closer the MD / TD modulus ratio is to 1.0, the smaller the anisotropy of the film.
As shown in Examples 2 and 13, when the styrene content is within the composition range of the present invention of the ethylene-styrene-divinylbenzene copolymer, the MD / TD elastic modulus ratio is close to 1.0, and the film anisotropy is I understand that it is small. On the other hand, in the sample of Comparative Example 5, the MD / TD elastic modulus ratio is large, that is, the film anisotropy is large.

<Expandability of film as dicing tape>
An adhesive material was applied to the film obtained by calendar molding in Example 13 to a thickness of 0.1 μm with a coater and adhered to the wafer. As the dicing condition, the expandability was examined by the degree of spread between the film and the chip when the substrate was cut to 40 μm in thickness and pushed up by 15 mm at room temperature. When the distance between the chips was measured at an arbitrary position on the wafer, the MD / TD ratio was 1.0 to 1.4 and the film anisotropy was small, and no cutting waste due to dicing cut was observed.

When the specific production conditions of the present invention are satisfied, a transparent cross copolymer with little film anisotropy can be efficiently synthesized. Since the cross-copolymer obtained by the production method of the present invention does not essentially contain chlorine, it is considered to have high environmental compatibility. Moreover, since the cross-copolymer obtained by the production method of the present invention does not essentially contain a plasticizer, it is considered to have high environmental compatibility.

4 is a TEM photograph of the cross copolymer obtained in Example 1. FIG. A film press-molded at 200 ° C. was used.

Claims (28)

A manufacturing method comprising a polymerization step comprising a coordination polymerization step and an anion polymerization step, wherein the coordination polymerization step comprises a single site arrangement comprising a transition metal compound represented by the following general formula (1) and a cocatalyst Copolymerization of ethylene monomer, aromatic vinyl compound monomer and aromatic polyene at a polymerization temperature of 80 ° C. or higher and 150 ° C. or lower using a coordination polymerization catalyst, aromatic vinyl compound unit content of 5 mol% or more and less than 15 mol%, An ethylene-aromatic vinyl compound-aromatic polyene copolymer having an aromatic polyene unit content of 0.01 mol% or more and 3 mol% or less and the remainder having an ethylene unit content was synthesized, and this ethylene- Using an anionic polymerization initiator in the presence of an aromatic vinyl compound-aromatic polyene copolymer and an anionic polymerizable vinyl compound monomer Method for producing a cross-copolymer which comprises polymerizing.


In the formula, A and B may be the same or different, and each is an unsubstituted or substituted benzoindenyl group represented by the general formula (2), (3), or (4), represented by the general formula (5). And a group selected from an unsubstituted or substituted indenyl group. In the following general formulas (2), (3), and (4), R1 to R3 are each hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an alkyl group having 7 to 20 carbon atoms. An aryl group, a halogen atom, an OSiR ₃ group, a SiR ₃ group or a PR ₂ group (wherein R represents a hydrocarbon group having 1 to 10 carbon atoms). R1s, R2s, and R3s may be the same or different from each other, and adjacent R1 and R2 groups may be combined to form a 5- to 8-membered aromatic ring or aliphatic ring. In the following general formula (5), R4 is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, a halogen atom, an OSiR ₃ group, SiR _3. Group or PR ₂ group (R represents a hydrocarbon group having 1 to 10 carbon atoms). R4 may be the same or different from each other.








Y has a bond with A and B, and additionally has hydrogen or a hydrocarbon group having 1 to 15 carbon atoms (may contain 1 to 3 nitrogen, oxygen, sulfur, phosphorus, or silicon atoms) as a substituent. A methylene group or a boron group; The substituents may be different or the same. Y may have a cyclic structure.
X is hydrogen, a hydroxyl group, a halogen, a C1-C20 hydrocarbon group, a C1-C20 alkoxy group, a silyl group having a C1-C4 hydrocarbon substituent, or a C1-C20 It is an amide group having a hydrocarbon substituent. Two Xs may have a bond.
M is zirconium, hafnium, or titanium. The mass ratio of the ethylene-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step is 40% by mass to 95% by mass with respect to the mass of the cross-copolymer finally obtained through the anionic polymerization step. The manufacturing method according to claim 1, wherein: The cross-copolymer obtained by the production method according to claim 1 or 2, wherein the haze of a 1 mm-thick sheet is 30% or less, or the total light transmittance is 75% or more. The cross-copolymer obtained by the production method according to claim 1 or 2, wherein an initial tensile elastic modulus is 10 MPa or more and 150 MPa or less. The cross-copolymer obtained by the production method according to claim 1, wherein the elastic recovery property shown below is 50% or more.
<Elastic recovery>
Return rate (%) evaluated by the return rate of elongation when the film (MD direction) was fixed for 10 minutes in a stretched state of 50% and then opened for 180 seconds. Calculate with the following formula.
Return rate (%) = (Elongation at 50% −Residual elongation after 180 seconds after stress release) / Elongation at 50% × 100 The cross-copolymer obtained by the production method according to claim 1 or 2, wherein a thickness reduction rate is 15% or less in a heat deformation test (75 ° C, 1.5 kg load) defined in JIS C3005 . In the Taber abrasion test, as a sheet-like molded body having a thickness of 2 mm, an H-22 abrasion wheel is used according to JIS K-6264, and the Taber abrasion amount when measured under the conditions of 1 kg load and 1000 revolutions is 100 mg or less. A cross-copolymer obtained by the production method according to claim 1 or 2. The thickness 10~300μm film film upon forming an anisotropic (initial tensile modulus ratio MD / TD) is 1.0 or more, prepared according to claim 1 or 2, characterized in that more than 2.0 A cross-copolymer obtained by the method . 2. The method for producing a cross copolymer according to claim 1, wherein the aromatic polyene compound is divinylbenzene. 2. The method for producing a cross copolymer according to claim 1, wherein the anion polymerizable vinyl compound monomer used in the anionic polymerization step is an aromatic vinyl compound monomer. The cross-copolymer according to claim 1, wherein a copolymer having a weight average molecular weight of not more than 150,000 and not less than 30,000 is used for the ethylene-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step. A method for producing a polymer. The aromatic vinyl compound monomer used in the coordination polymerization step is styrene, and the anion polymerizable vinyl compound monomer used in the anion polymerization step is styrene, part or all of which is unreacted styrene in the coordination polymerization step. The method for producing a cross copolymer according to claim 1, wherein: 2. The method for producing a cross copolymer according to claim 1, wherein the anionic polymerization initiator used in the anionic polymerization step is butyl lithium. A resin composition comprising a cross-copolymer obtained by the production method of claim 1 and an aromatic vinyl compound polymer. A resin composition comprising a cross-copolymer obtained by the production method according to claim 1 and an olefin polymer. A resin composition comprising a cross-copolymer obtained by the production method according to claim 1, an aromatic vinyl compound polymer, and an olefin polymer. A resin composition comprising a cross copolymer obtained by the production method of claim 1 and a block copolymer polymer. The molded object which consists of a cross-copolymer obtained by the manufacturing method of Claim 1. A film or sheet comprising a cross-copolymer obtained by the production method of claim 1. The film or sheet according to claim 19, wherein the initial tensile modulus ratio (MD / TD) in the MD direction and the TD direction is 1.0 or more and 2.0 or less. The molded object which consists of a resin composition as described in any one of Claims 14-17. A film or sheet comprising the resin composition according to any one of claims 14 to 17. A tape substrate using the film according to claim 19 or 22. A tube comprising a cross-copolymer obtained by the production method of claim 1. A tube comprising the resin composition according to any one of claims 14 to 17. A resin composition comprising 70% by mass or more and 99% by mass or less of a cross-copolymer obtained by the production method of claim 1 and 1% by mass or more and 30% by mass or less of a petroleum resin or hydrogenated petroleum resin. The foam material which consists of a resin composition as described in any one of Claims 14-17. An electric wire covering material comprising the resin composition according to any one of claims 14 to 17.