JP5891229B2 - Skin material sheet - Google Patents

Description

  The present invention relates to a skin material sheet formed from a thermoplastic resin composition comprising a specific cross copolymer and an ethylene-based copolymer.

  Various types of functionality are required in addition to various levels of softness for skin materials located between humans and various hard vehicles such as passenger cars, furniture, indoor interiors, and even robots. For example, automotive interior skin materials include heat resistance, weather resistance, cold resistance, texture retention including heat history during molding, scratch resistance against human contact, and oil resistance to chemical substances accompanying humans. Chemical resistance is required.

  Conventionally, a skin material made of soft PVC to which a plasticizer is added has been used in such a field. Soft PVC is a material with excellent softness, oil resistance and scratch resistance, and is advantageous in terms of price, but it is a problem of management at the time of incineration, VOC due to plasticizers contained in large quantities in recent years, and some plasticizers However, there is a demand for materials that are more environmentally friendly in terms of environmental hormone concerns and the heavy metal stabilizers included. Therefore, skin materials made of TPO (olefin-based thermoplastic elastomer) and TPS (styrene-based thermoplastic elastomer) have attracted attention, and are characterized by heat resistance, softness, recyclability, and environmental friendliness. It was. These materials are desired to be improved in that they are scratch resistant and have insufficient wear resistance. When cross-linked ethylene-propylene rubber (TPO) used as a soft component or cross-linked or non-cross-linked styrene hydrogenated block copolymer (TPS) does not have sufficient oil resistance, causing swelling and deformation in the above harsh environment There is. If the abrasion resistance with scratches is improved by reducing the amount of PP added, etc., the heat resistance, particularly the surface wrinkle retention at the time of sheet molding, may be lowered and wrinkles may disappear. Further, when crosslinking is performed on a soft component and / or a hard component, the cost is increased, and improvement is desired in terms of odors derived from various crosslinking materials and auxiliaries.

  Against this background, we have proposed a new soft resin, a styrene-ethylene cross copolymer (Patent Documents 1, 2, and 3). This resin is characterized by a wide range of hardness adjustment from soft to semi-rigid without a plasticizer, and excellent scratch resistance and oil resistance. However, the present resin itself lacks heat resistance for the above-mentioned applications, and further improvement is desired in terms of the retention of wrinkles during use as a skin material or during molding. From such a background, heat resistance has been improved by blending heat-resistant resins. When PP is added, the scratch resistance and wear resistance is reduced, as in TPO and TPS. Therefore, heat resistance is improved by the addition of PPE (polyphenylene ether) resin (Patent Document 4) and the addition of TPEE (Polyester soft resin) (Patent Document 5).

On the other hand, electron beam cross-linking of an ethylene-styrene copolymer is known. For example, Patent Documents 6 to 8 describe an electron beam cross-linked body of an ethylene-styrene copolymer. Patent Document 9 describes that the electron beam crosslinkability is improved by copolymerizing an alkyl-substituted styrene with the same cross-copolymer as in the present application.
The following documents are each incorporated herein by reference.
No. 00/037517 WO2007139116 JP 2009-102515 A WO2009-128444 Japanese Patent Application No. 2009-094556 Japanese Patent Publication No. 3-60123 JP-A-8-73668 WO99-10395 Japanese Unexamined Patent Publication No. 2011-74187

  However, when PPE is added, abrasion resistance and oil resistance are further improved, but because of the higher level of heat resistance, increasing the blending amount increases the hardness and lowers the flow, depending on the application. Improvement is desired in that it decreases. On the other hand, in the case of addition of TPEE, an improvement is desired in that if the blending amount is increased due to a higher level of heat resistance, the abrasion resistance with scratches is reduced. Therefore, there is a need for a method of imparting sufficient heat resistance, particularly wrinkle retention, to withstand use and molding, while taking advantage of the excellent scratch-resistant wear resistance, oil resistance, and calendar and extrusion processability of the cross-copolymer. Has been. However, copolymerization of alkyl-substituted styrene with a cross-copolymer requires complicated steps such as side reaction control during anionic polymerization, and is not always satisfactory industrially.

  Patent Documents 1, 2, and 3 describe cross-copolymer electron beam cross-linked bodies, particularly tape base materials, electric wire coating materials, and foaming agents. However, there has been no known material having a composition that gives an industrially advantageous low irradiation dose, and in particular, sufficient retainability as a skin material sheet. In addition, the skin material sheet is subjected to decoration such as a texture, and then a base material and, if necessary, a step of attaching to the foam sheet is required. In this case, the skin material is heated and the texture disappears or fades. Alternatively, improvement has been desired in terms of glossiness. In addition, regarding the texture retention, the conditions for appropriate electron beam irradiation have not been known.

An object of the present invention is to provide a skin sheet having excellent energy beam crosslinking characteristics and excellent softness, mechanical properties, heat resistance, and texture retention.
That is, according to this invention, the sheet | seat formed by bridge | crosslinking a thermoplastic resin composition by energy ray irradiation is provided. The said sheet | seat is used suitably as a sheet | seat for skin materials. Moreover, the skin material containing the said sheet | seat is also provided.
The thermoplastic resin composition comprises, as a resin component, 20 to 90 parts by mass of the cross copolymer A and 80 to 10 parts by mass of the ethylene copolymer B, for a total of 100 parts by mass. Here, the cross-copolymer A is obtained by a production method including a polymerization step comprising a coordination polymerization step and a subsequent cross-linking step. On the other hand, the ethylene-based copolymer B is an ethylene-olefin copolymer and / or an ethylene-unsaturated carboxylic acid or ester copolymer thereof.

In one embodiment of the present invention, the coordination polymerization step is a process of copolymerizing an olefin monomer, an aromatic vinyl compound monomer, and an aromatic polyene using a single site coordination polymerization catalyst, thereby producing an olefin-aromatic vinyl compound. A process for synthesizing an aromatic polyene copolymer, and the cross-linking process is an anionic polymerization initiator or radical in which an olefin-aromatic vinyl compound-aromatic polyene copolymer and an aromatic vinyl compound monomer coexist This is a step of polymerizing using a polymerization initiator.
The composition of the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step is preferably an aromatic vinyl compound content of 5 mol% to 30 mol%, and an aromatic polyene content of 0.01 mol. % To 0.3 mol%, the balance being the olefin content.
The mass ratio of the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step with respect to the cross copolymer obtained in the crossing step is preferably 50 to 99% by mass.

  The thermoplastic resin composition is excellent in energy beam crosslinking characteristics. A sheet obtained by crosslinking the thermoplastic resin composition by irradiation with energy rays is excellent in softness, mechanical properties, heat resistance, and texture retention.

[Explanation of terms]
The “single site coordination polymerization catalyst” in the present specification is a polymerization catalyst composed of a transition metal compound and a promoter. This includes, for example, a metallocene catalyst, a half metallocene catalyst, a soluble Ziegler-Natta catalyst, or an FI (pheniximine) catalyst.

  “Substitution” in the present specification means a substituent that is generally used for each compound within a range not impairing the effects of the present invention, and is not limited thereto. Substitution with a hydrocarbon group having 1 to 3 carbon atoms is included.

  The “storage elastic modulus (E ′)” in the present specification is a storage elastic modulus that can be measured by a dynamic viscoelasticity measuring device at 1 Hz and a temperature increase rate of 4 ° C./min.

  Further, in the present specification, “including” includes “consisting mainly of”, “consisting essentially of” and “consisting of”, and “consisting mainly of” includes “consisting essentially of” and “Consisting of” is included, and “consisting essentially of” includes “consisting of”.

  In the present specification, “consisting mainly of” is not limited to this, but the target component mentioned is 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass of the total mass. % Or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, or 99% by mass or more or 100%.

  Each numerical range in this specification includes an upper limit value and a lower limit value indicated by “to” and “from”, respectively. For example, the descriptions “A to B” and “A to B” mean that they are A or more and B or less. In addition, the descriptions “A to B”, “A to B”, and “A or more and B or less”, when used as a preferable range, independently indicate that “A or more is preferable” and “B or less Is preferable ”.

Embodiment
Hereinafter, although the present invention is explained in detail using the form for carrying out the present invention, the present invention is not limited to this.

In one embodiment of the present invention, a thermoplastic resin composition comprising a total of 100 parts by mass of 20 to 90 parts by mass of the cross copolymer A and 80 to 10 parts by mass of the ethylene copolymer B is irradiated with energy rays. A sheet for a skin material formed by crosslinking with
(1) The cross copolymer A is
(I) An arrangement for synthesizing an olefin-aromatic vinyl compound-aromatic polyene copolymer by copolymerizing an olefin monomer, an aromatic vinyl compound monomer and an aromatic polyene using a single site coordination polymerization catalyst. A coordination polymerization step;
(Ii) a cross-linking step in which the olefin-aromatic vinyl compound-aromatic polyene copolymer and the aromatic vinyl compound monomer coexist and polymerized using an anionic polymerization initiator or a radical polymerization initiator;
Obtained by a production method comprising a polymerization step comprising:
(2) The composition of the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step has an aromatic vinyl compound content of 5 mol% to 30 mol% and an aromatic polyene content of 0.01 mol%. Not less than 0.3 mol% and the balance is olefin content;
(3) The mass ratio of the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step relative to the cross copolymer obtained in the cross-linking step is 50 to 99% by mass;
(4) The ethylene-based copolymer B is a sheet for a skin material characterized by being an ethylene-olefin copolymer and / or a copolymer of ethylene-unsaturated carboxylic acid or ester thereof.
The sheet is excellent in energy beam cross-linking properties, softness, mechanical properties, heat resistance, and texture retention. In addition, it has excellent scratch resistance and abrasion resistance.

<Cross copolymer A>
In the cross copolymer A according to the above embodiment, the main chain is an olefin-aromatic vinyl compound-aromatic polyene copolymer, and a polymer chain composed of an aromatic vinyl compound monomer that is a cross chain is the main chain. It is thought that the structure (cross-copolymerization structure or Segregated star copolymer structure) couple | bonded through the chain | strand aromatic polyene unit is included. As long as it is obtained by the above production method and is within the range of the above composition, the structure and the proportion of the present cross copolymer A are arbitrary as long as the effects of the present invention are not impaired.
The MFR value of the cross copolymer A of the present invention measured at 200 ° C. and a load of 98 N is not particularly limited, but is generally 0.01 g / 10 min or more and 300 g / 10 min or less.

  Examples of the olefin used in the coordination polymerization step include, but are not limited to, ethylene and α-olefins having 3 to 20 carbon atoms. These are used alone or in combination of two or more. be able to. Examples of the α-olefin having 3 to 20 carbon atoms include chain olefins such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and vinylcyclohexane, and cyclopentene and norbornene. Of cyclic olefins. In the coordination polymerization step, ethylene or a mixture of ethylene and α-olefin is preferably used, and ethylene is more preferably used.

  The aromatic vinyl compound monomer used in the coordination polymerization step is not limited to this, but examples thereof include styrene and substituted styrene, and these can be used alone or in combination of two or more. . Examples of the substituted styrene include p-methylstyrene, m-methylstyrene, o-methylstyrene, ot-butylstyrene, mt-butylstyrene, pt-butylstyrene, p-chlorostyrene, o- Chlorostyrene and the like are included. In the coordination polymerization step, styrene is preferably used alone industrially.

  The aromatic polyene used in the coordination polymerization step is not limited to this. For example, the aromatic polyene has 10 to 30 carbon atoms, and has a plurality of double bonds (vinyl group) and one or more carbon atoms. An aromatic polyene having an aromatic group and capable of coordination polymerization, wherein one of the double bonds (vinyl group) is used for coordination polymerization and polymerized, and the remaining double bond is anionic polymerization or Aromatic polyenes capable of radical polymerization are mentioned. In the coordination polymerization step, for example, any one or a mixture of two or more of orthodivinylbenzene, paradivinylbenzene and metadivinylbenzene can be suitably used.

  The composition of the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the above coordination polymerization step has an aromatic vinyl compound content of 5 mol% to 30 mol%, and an aromatic polyene content of 0.01 mol% to 0 mol. When the content of olefin is 3 mol% or less and the balance is the olefin content, a cross copolymer having high softness (for example, A hardness of 95 or less, etc.) can be obtained. If the aromatic vinyl compound content is lower than 5 mol%, the softness may be lost due to ethylene crystallinity, and if it is higher than 30 mol%, the present olefin-aromatic vinyl compound-aromatic polyene copolymer will be lost. Glass transition temperature becomes higher than 0 degreeC, and the softness | flexibility in low temperature will fall. The composition of the olefin-aromatic vinyl compound-aromatic polyene copolymer can be achieved by a known general control method, but it can be most easily achieved by changing the monomer charge composition ratio.

  When the composition of the olefin-aromatic vinyl compound-aromatic polyene copolymer is an aromatic vinyl compound content of 5 mol% or more, a crystal structure derived from an olefin chain structure, for example, a crystal structure based on an ethylene chain or a propylene chain It can be reduced, the softness of the resin composition of the present invention finally obtained can be enhanced, shrinkage due to crystallization during molding can be prevented, and the dimensional stability of the molded body can be more reliably maintained. If the content of the aromatic vinyl compound is 10 mol% or more, the effect can be obtained more reliably, and therefore, it is more preferable. The cross copolymer A according to the present invention has a total crystal melting heat including the olefin crystallinity and other crystallinity of preferably 100 J / g or less, and more preferably 50 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 approximately 200 ° C. by DSC.

  When the composition of the olefin-aromatic vinyl compound-aromatic polyene copolymer has an aromatic vinyl compound content of 30 mol% or less, excellent energy beam crosslinking characteristics are exhibited. The aromatic vinyl compound content is preferably 25 mol% or less, and the effect can be more reliably exhibited.

  The aromatic polyene content of the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step is 0.01 mol% or more and 0.3 mol% or less, preferably 0.01 mol% or more. It is 0.1 mol% or less. If the aromatic polyene content is not less than the above lower limit, the properties as the cross-copolymer A of the present invention can be more reliably exhibited. If the aromatic polyene content is not more than the above upper limit, the moldability is improved. Can keep.

  With respect to the cross copolymer A in the above form, the weight ratio of the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step is 50% by mass or more and 99% by mass of the weight of the cross copolymer A. The following is preferable. If the mass ratio (mass%) of the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization process to the cross copolymer A is 50 mass% or more, the softness is increased and the electrons are increased. The wire crosslinkability is improved and the texture is excellent. This ratio is preferably 90% by mass or less, and in this case, the heat resistance after electron beam crosslinking can be exhibited, and for example, the creep start temperature can be 150 ° C. or higher. The above ratio is more preferably 60% by mass or more and 90% by mass or less. In this case, a cross copolymer having particularly excellent softness is obtained, and the resin composition is excellent in softness (for example, A hardness 95 or less). You can get things. In addition, the above ratios are determined by sampling and analyzing a part of the polymerization solution at the end of coordination polymerization, and the cross-copolymerization obtained by sampling and analyzing a part of the polymerization solution after anionic polymerization. It can be determined from the combined mass. Or the said ratio can also be calculated | required by comparing the composition of the main chain olefin-aromatic vinyl compound-aromatic polyene copolymer with the composition of the obtained cross-copolymer A.

  The weight average molecular weight of the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step is preferably 1,000,000 or less and 30,000 or more, but the molding processability of the resin composition of the present invention is improved. In consideration, it is more preferably 30,000 or more and 300,000 or less. The molecular weight distribution (Mw / Mn) of the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step is preferably 1.5-8, more preferably 1.5-6. Most preferably, it is 1.5 or more and 4 or less. When molecular weight distribution is below this upper limit, the self-crosslinking of the polyene part of an olefin-aromatic vinyl compound-aromatic polyene copolymer can be suppressed, and deterioration of molding processability and gelation can be prevented.

  The aromatic vinyl compound monomer used in the crossing step is not limited to this, but examples thereof include p-methylstyrene, p-tert-butylstyrene, p-chlorostyrene, α-methylstyrene, vinyl. Naphthalene, vinyl anthracene and the like can be mentioned, and these can be used alone or in combination of two or more. The aromatic vinyl compound monomer used in the crossing step is preferably styrene. The aromatic vinyl compound monomer used in the coordination polymerization step and the aromatic vinyl compound monomer used in the crossing step are preferably the same, and one of the aromatic vinyl compound monomers used in the crossing step is one. More preferably, part or all of the monomer is an unreacted aromatic vinyl compound monomer in the coordination polymerization step. Most preferably, the aromatic vinyl compound monomer used in the coordination polymerization step is styrene, and the aromatic vinyl compound monomer used in the cross-linking step is styrene, part or all of which is the coordination polymerization step. In the unreacted styrene.

In the crossing step, in addition to the aromatic vinyl compound monomer, a monomer capable of anionic polymerization or radical polymerization may be added. The addition amount is preferably up to an equimolar amount with respect to the amount of the aromatic vinyl compound monomer used.
In the cross-linking step, in addition to the monomer, aromatic polyene that is not polymerized in the coordination polymerization step and remains in a small amount in the polymerization solution may also be polymerized.

  The length (molecular weight) of the cross chain portion of the cross-copolymer A can be estimated from the molecular weight of the homopolymer that has not been cross-linked, and the length is preferably 5000 or more and 15 as the weight average molecular weight. It is 10,000 or less, more preferably 5000 or more and 100,000 or less, particularly preferably 5000 or more and 70,000 or less. The molecular weight distribution (Mw / Mn) is preferably 5 or less, more preferably 3 or less, and particularly preferably 2 or less.

<Ethylene copolymer B>
As the ethylene-based copolymer B according to the above form, an ethylene-olefin copolymer, that is, a copolymer of ethylene and one or more olefins is preferably used. Such an olefin is not limited to this, but an aliphatic or alicyclic α-olefin having 3 to 20 carbon atoms or a cyclic olefin is preferably used. Examples of the aliphatic α-olefin include propylene, 1-butene, 1-hexene, and 1-octene. Examples of the alicyclic α-olefin include vinylcyclohexane. Examples of the cyclic olefin include norbornene. It is. The specific gravity of the ethylene copolymer is preferably 0.91 or less and 0.84 or more. The ethylene content in the ethylene and olefin copolymer satisfying such a range is generally in the range of 60 to 90% by mass. When the specific gravity of the present ethylene copolymer is 0.91 or less, high energy beam crosslinking characteristics can be obtained, and the softness and scratch resistance of the finally obtained skin material sheet can be kept good. If the specific gravity of the present ethylene copolymer is 0.84 or more, the mechanical properties of the finally obtained resin composition can be kept high. The MFR of the ethylene copolymer measured at 200 ° C. and 98 N is not particularly limited, but is preferably in the range of 0.2 to 30 g / 10 minutes. When the MFR is 0.2 g / 10 min or more, better moldability can be maintained. When the MFR is 30 g / 10 min or less, the energy beam cross-linking property is high, and the wrinkle flow and wrinkle disappearance during the molding process. The possibility can be further reduced.

  As the ethylene-based copolymer B according to the above form, a copolymer of ethylene-unsaturated carboxylic acid or ester thereof, that is, a copolymer of ethylene and one or more unsaturated carboxylic acids or esters thereof can also be used. . Specific examples of such unsaturated carboxylic acids or esters thereof include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, isopropyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, A glycidyl methacrylate etc. can be illustrated. The preferable ethylene content in the copolymer of ethylene and unsaturated carboxylic acid or ester thereof is generally in the range of 60 to 90% by mass. If the ethylene content is 90% by mass or less, the softness and scratch resistance of the finally obtained resin composition sheet can be kept better. Moreover, if the ethylene content is 60% by mass or more, the mechanical properties of the finally obtained resin composition can be kept better.

  In the present invention, the ethylene copolymer B is one or more copolymers of ethylene and olefins, or one or more copolymers of ethylene and unsaturated carboxylic acids or esters thereof. These ethylene and olefins are used. A copolymer of ethylene and an unsaturated carboxylic acid or ester thereof may be used in combination.

Below, the manufacturing method of this invention is demonstrated in detail.
<Coordination polymerization process>
As the single-site coordination polymerization catalyst according to the present invention, any single-site coordination catalyst can be used as long as the effects of the present invention are not impaired. Preferably, the following general formula (1) or (2) The transition metal compound represented by these is used.

上式中、Ａ、Ｂは同一でも異なっていてもよく、非置換もしくは置換ベンゾインデニル基、非置換もしくは置換シクロペンタジエニル基、非置換もしくは置換インデニル基、または非置換もしくは置換フルオレニル基から選ばれる。好ましくは、Ａ、Ｂは非置換もしくは置換ベンゾインデニル基、非置換もしくは置換インデニル基から選ばれる。
Ｙは、Ａ、Ｂと結合を有し、他に置換基として水素もしくは炭素数１〜１５の炭化水素基（１〜３個の窒素、酸素、硫黄、燐、珪素原子を含んでもよい）を有するメチレン基である。置換基は互いに異なっていても同一でもよい。また、Ｙは環状構造を有していてもよい。
Ｘは、水素、水酸基、ハロゲン、炭素数１〜２０の炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜４の炭化水素置換基を有するシリル基、または炭素数１〜２０の炭化水素置換基を有するアミド基である。Ｘが複数の場合、Ｘ同士は結合を有しても良い。
Ｍはジルコニウム、ハフニウム、またはチタンである。
ｎは、１または２の整数である。

In the above formula, A and B may be the same or different, and are derived from an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, or an unsubstituted or substituted fluorenyl group. To be elected. Preferably, A and B are selected from an unsubstituted or substituted benzoindenyl group and an unsubstituted or substituted indenyl group.
Y has a bond with A and B, and in addition, hydrogen or a hydrocarbon group having 1 to 15 carbon atoms (including 1 to 3 nitrogen, oxygen, sulfur, phosphorus, or silicon atoms) as a substituent. It has a methylene group. The substituents may be different or the same. Y may have a cyclic structure.
X is hydrogen, a hydroxyl group, 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. When X is plural, Xs may have a bond.
M is zirconium, hafnium, or titanium.
n is an integer of 1 or 2.

  Preferred examples of the transition metal compound include substituted methylene bridge structures specifically exemplified in EP-087492A2 publication, JP-A-11-130808, and JP-A-9-309925, each of which is incorporated herein by reference. And transition metal compounds having a boron crosslinking structure specifically exemplified in WO 01/068719, which is incorporated herein by reference.

上式中、Ｃｐは非置換もしくは置換シクロペンタフェナンスリル基、非置換もしくは置換ベンゾインデニル基、非置換もしくは置換シクロペンタジエニル基、非置換もしくは置換インデニル基、または非置換もしくは置換フルオレニル基から選ばれる。
Ｙ’は、Ｃｐ、Ｚと結合を有し、他に置換基として水素もしくは炭素数１〜１５の炭化水素基（１〜３個の窒素、酸素、硫黄、燐、珪素原子を含んでもよい）を有するメチレン基、シリレン基、エチレン基、ゲルミレン基、もしくは硼素残基である。置換基は互いに異なっていても同一でもよい。また、Ｙ’は環状構造を有していてもよい。
Ｚは窒素、酸素またはイオウを含み、窒素、酸素またはイオウでＭ’に配位する配位子であって、Ｙ’と結合を有し、他に置換基として水素もしくは炭素数１〜１５の炭化水素基（１〜３個の窒素、酸素、硫黄、燐、珪素原子を含んでもよい）を有する。
Ｘ’は、水素、ハロゲン、炭素数１〜１５のアルキル基、炭素数６〜１０のアリール基、炭素数８〜１２のアルキルアリール基、炭素数１〜４の炭化水素置換基を有するシリル基、炭素数１〜１０のアルコキシ基、または炭素数１〜６のアルキル置換基を有するジアルキルアミド基である。
Ｍ’はジルコニウム、ハフニウム、またはチタンである。
ｎは、１または２の整数である。

In the above formula, Cp is an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, or an unsubstituted or substituted fluorenyl group. Chosen from.
Y ′ has a bond with Cp and Z, and as a substituent, hydrogen or a hydrocarbon group having 1 to 15 carbon atoms (may contain 1 to 3 nitrogen, oxygen, sulfur, phosphorus, or silicon atoms) And a methylene group, a silylene group, an ethylene group, a germylene group, or a boron residue. The substituents may be different or the same. Y ′ may have a cyclic structure.
Z is a ligand containing nitrogen, oxygen or sulfur, coordinated to M ′ with nitrogen, oxygen or sulfur, having a bond with Y ′, and additionally having hydrogen or a carbon number of 1 to 15 as a substituent. It has a hydrocarbon group (may contain 1 to 3 nitrogen, oxygen, sulfur, phosphorus and silicon atoms).
X ′ is hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms, or a silyl group having a hydrocarbon substituent having 1 to 4 carbon atoms. , An alkoxy group having 1 to 10 carbon atoms, or a dialkylamide group having an alkyl substituent having 1 to 6 carbon atoms.
M ′ is zirconium, hafnium, or titanium.
n is an integer of 1 or 2.

  In the present coordination polymerization step, more preferably, a polymerization catalyst comprising a single site coordination polymerization catalyst and a co-catalyst, particularly preferably a single site coordination polymerization catalyst represented by the above general formula (1) A polymerization catalyst composed of a cocatalyst is used.

  As the co-catalyst used in the present coordination polymerization step, a known co-catalyst conventionally used in combination with a transition metal compound can be used as long as the object of the present invention is not impaired. Examples of the aluminoxane include, but are not limited to, alumoxane or boron compounds such as methylaluminoxane (or methylalumoxane or MAO) and the like are preferably used. Further examples of cocatalysts used are EP-08749292A2, JP-A-11-130808, JP-A-9-309925, WO00 / 20426, EP0985689A2, each incorporated herein by reference. Examples thereof include promoters and alkylaluminum compounds described in JP-A-6-184179. The transition metal compound and the cocatalyst may be mixed and prepared outside the polymerization equipment, or may be mixed inside the equipment at the time of polymerization.

When alumoxane or the like is used as a co-catalyst, it is used at a ratio of 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 this ratio is larger than 0.1, the transition metal compound can be activated more effectively, and if it is 100,000 or less, it is economically advantageous.
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 this ratio is larger than 0.01, the transition metal compound can be activated more effectively, and if it is 100 or less, it is economically advantageous.

In the production of the olefin-aromatic vinyl compound-aromatic polyene copolymer in this coordination polymerization step, the above-mentioned various monomers and catalyst are brought into contact with each other. Can be used.
As a copolymerization method, a method of polymerizing 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, etc. A method using a saturated aliphatic or aromatic hydrocarbon or halogenated hydrocarbon alone or in a mixed solvent can be used. Preferably, a mixed alkane solvent, cyclohexane, toluene, or ethylbenzene is used as the solvent. 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 are a variety of well-known cooling devices such as dynamic or static mixers and various known mixers such as static mixers that also remove heat, and coolers equipped with thin tubes for heat removal. You may have a vessel. Moreover, you may have a batch type prepolymerization can. Furthermore, methods such as gas phase polymerization can also be used.

The polymerization temperature is preferably -78 ° C to 200 ° C. When the polymerization temperature is −78 ° C. or higher, it is industrially advantageous, and when it is 200 ° C. or lower, the decomposition of the transition metal compound can be suppressed. The polymerization temperature is more preferably industrially preferably from 0 ° C to 160 ° C, particularly preferably from 30 ° C to 160 ° C.
The pressure at the time of polymerization is preferably 0.1 to 100 atm, more preferably 1 to 30 atm, particularly industrially particularly preferably 1 to 10 atm.

  The transition metal compound of the single site coordination polymerization catalyst used in this production method has a structure represented by the general formula (1), and A and B are unsubstituted or substituted benzoindenyl groups, unsubstituted or substituted indenyl groups. Y is bonded to A and B, and hydrogen or a hydrocarbon group having 1 to 15 carbon atoms (1 to 3 nitrogen, oxygen, sulfur, phosphorus, silicon atoms) And the transition metal compound is a racemate, the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained by this production method is an olefin- An alternating structure of an aromatic vinyl compound, preferably an ethylene-aromatic vinyl compound alternating structure, has isotactic stereoregularity, so that the cross-copolymer of the present invention has the present alternating structure. It can have a microcrystalline from which it is derived. In this case, the present olefin-aromatic vinyl compound-aromatic polyene copolymer has better mechanical properties and oil resistance based on the microcrystallinity of the alternating structure as compared with the case without stereoregularity. Features can ultimately be inherited by the cross-copolymers of the present invention.

  The crystal melting point due to the microcrystalline nature of the alternating structure of olefin-aromatic vinyl compound-aromatic polyene copolymer is generally in the range of 50 ° C. to 120 ° C., and the heat of crystal melting by DSC is generally 1-30 J / g or less. Therefore, the cross copolymer A of the present invention as a whole can preferably have a heat of crystal fusion of 50 J / g or less, more preferably 30 J / g or less. The crystallinity of the heat of crystal melting within this range does not adversely affect the softness and molding processability of the present cross copolymer A, but rather is advantageous in terms of excellent mechanical properties.

<Cross forming process>
In the crossing step of the production method of the present invention, the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step and the aromatic vinyl compound monomer are allowed to coexist, and an anionic polymerization initiator or radical polymerization is performed. Anionic polymerization or radical polymerization is performed using an initiator.

When anionic polymerization is employed in the crossing step, 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.
The solvent is not limited to this, but a mixed alkane solvent that does not cause inconvenience such as chain transfer or a solvent such as cyclohexane or benzene is particularly preferable. If the polymerization temperature is 150 ° C. or lower, toluene, ethylbenzene, etc. Other solvents can also be suitably used.

When radical polymerization is employed in the crossing step, a known radical polymerization initiator that can be used for polymerization or copolymerization of an aromatic vinyl compound can be used. As such examples, a peroxide (peroxide), an azo polymerization initiator, and the like can be freely selected by those skilled in the art as needed. Such examples are described in the Japanese fat catalog organic peroxides 10th edition (http://www.nof.co.jp/business/chemical/pdf/product01/Catalog_all.), Each of which is incorporated herein by reference. downloadable from pdf), Wako Pure Chemicals catalog, etc., and can be obtained from these companies.
Although there is no restriction | limiting in particular in the usage-amount of a polymerization initiator, 0.001-5 mass parts is used suitably with respect to 100 mass parts of monomers. In the case of using an initiator such as a peroxide (peroxide) or an azo polymerization initiator, or a curing agent, the curing treatment is performed at an appropriate temperature and time in consideration of its half-life. The conditions in this case are arbitrary according to the initiator and the curing agent, but generally a temperature range of about 50 ° C. to 150 ° C. is preferable. Furthermore, in this radical polymerization step, a known chain transfer agent can be used mainly for the purpose of controlling the molecular weight of the cross chain. Examples of such chain transfer agents include, but are not limited to, mercaptan derivatives such as t-dodecyl mercaptan, α-styrene dimer, and the like.
The solvent is particularly preferably an alkane solvent or a solvent such as cyclohexane or benzene, but other solvents such as toluene or ethylbenzene can also be used.

  In the cloth-forming step of the present invention, a higher copolymerization rate of the aromatic vinyl compound monomer can be obtained as a cross-copolymer having preferable mechanical properties and optical properties. For this reason, anionic polymerization that can easily achieve a high polymerization conversion rate of the aromatic vinyl compound monomer in a relatively short time is preferably employed.

  The crossing step of the present invention is carried out after the 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 crossing step. However, it is economically preferable to use the residual olefin from the polymerized solution after the coordination polymerization in the next crossing step after releasing or without releasing the residual olefin. It is also one of the features of the present invention that the polymer solution containing the polymer can be used in the cloth forming step without separating the polymer from the polymerization solution.

As the polymerization method and form, any known one used for radical or anionic polymerization can be used. A polymerization temperature of −78 ° C. to 200 ° C. is preferably used. If the polymerization temperature is −78 ° C. or higher, it is industrially advantageous, and if it is 200 ° C. or lower, chain transfer and the like can be suppressed. The polymerization temperature is particularly preferably 30 ° C to 150 ° C.
The pressure at the time of polymerization is preferably 0.1 to 100 atm, more preferably 1 to 30 atm, particularly industrially particularly preferably 1 to 10 atm.

<Additives>
In the thermoplastic resin composition of the present invention, in addition to the above-mentioned cross copolymer A and ethylene-based copolymer B, additions that are used for ordinary resins as necessary within the range not impairing the object of the present invention Agents, for example, plasticizers, inorganic fillers (fillers), flame retardants, weathering agents, heat stabilizers, antioxidants, antistatic agents, light fasteners, UV absorbers, anti-aging agents, fillers, colorants Further, a lubricant, an antifogging agent, a foaming agent, a flame retardant aid and the like may be added. Some of these are exemplified below. Since the cross-copolymer used in the thermoplastic resin composition of the present invention generally has a relatively good affinity and compatibility with these additives, the resulting energy beam cross-linked product of the thermoplastic resin composition is It is relatively soft and has the characteristics of excellent abrasion resistance and heat resistance.
In this case, the compounding amount of each additive is in the range when described below, and in the range of 0 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition unless otherwise specified. It is preferable to be used.

<Plasticizer>
The thermoplastic resin composition of the present invention can be blended with any known plasticizer conventionally used for vinyl chloride and other resins. Suitable plasticizers are, for example, hydrocarbon plasticizers or oxygen-containing or nitrogen-containing plasticizers. Examples of hydrocarbon plasticizers (oils) include aliphatic hydrocarbon plasticizers, aromatic hydrocarbon plasticizers and naphthenic plasticizers. Examples of oxygen-containing or nitrogen-containing plasticizers include ester-based plasticizers. Examples thereof include an agent, an epoxy plasticizer, an ether plasticizer, and an amide plasticizer.
These plasticizers can be used to adjust the hardness or fluidity (molding processability) of the thermoplastic resin composition of the present invention. Moreover, these plasticizers have the effect of lowering the glass transition temperature and lowering the embrittlement temperature.

Examples of ester plasticizers that can be suitably used in the present invention include, but are not limited to, phthalic acid esters, trimellitic acid esters, adipic acid esters, sebacic acid esters, and azelate esters. , Citric acid esters, acetyl citrate esters, glutamic acid esters, succinic acid esters, acetic acid esters and other mono fatty acid esters, phosphoric acid esters and polyesters thereof.
Examples of the epoxy plasticizer that can be suitably used in the present invention include, but are not limited to, epoxidized soybean oil and epoxidized linseed oil.
Examples of ether plasticizers that can be suitably used in the present invention include, but are not limited to, polyethylene glycol, polypropylene glycol, copolymers thereof, and mixtures thereof. .
Examples of the amide plasticizer that can be suitably used in the present invention include, but are not limited to, sulfonic acid amides.
These plasticizers may be used alone or in combination.

  An ester plasticizer is particularly preferably used in the present invention. The ester plasticizer has the advantages of excellent compatibility with the cross-copolymer, excellent plasticizing effect (high degree of glass transition temperature reduction), and less bled. Generally, the compounding amount of the plasticizer is 1 to 25 parts by mass, preferably 1 to 15 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition of the present invention. If it is blended in an amount of 1 part by mass or more, the effect as a plasticizer can be expected more reliably, and if it is 25 parts by mass or less, it suppresses bleeding, excessive softening, and excessive stickiness. can do.

<Inorganic filler (Filler)>
Hereinafter, the inorganic filler that can be used in the present invention will be described.
The inorganic filler is also used for imparting flame retardancy to the thermoplastic resin composition of the present invention. The volume average particle diameter of the inorganic filler is preferably 50 μm or less, preferably 10 μm or less, and preferably 0.5 μm or more. If the volume average particle diameter is 0.5 μm or more and 50 μm or less, it is possible to suppress a decrease in mechanical properties (tensile strength, elongation at break, etc.), a decrease in flexibility and the occurrence of pinholes when formed into a film. it can. The volume average particle diameter is a volume average particle diameter measured by a laser diffraction method.

Examples of inorganic fillers include, but are not limited to, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, triphenyl phosphate, ammonium polyphosphate. , Polyphosphate amide, zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, molybdenum oxide, guanidine phosphate, hydrotalcite, snakerite, zinc borate, anhydrous zinc borate, zinc metaborate, barium metaborate, antimony oxide, three Antimony oxide, antimony pentoxide, red phosphorus, talc, alumina, silica, boehmite, bentonite, sodium silicate, calcium silicate, calcium sulfate, calcium carbonate, magnesium carbonate, and one or more compounds selected from these The It is possible to use. 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.
As for the compounding quantity of an inorganic filler, 1-1000 mass parts is preferable with respect to 100 mass parts of the thermoplastic resin composition of this invention, More preferably, it is the range of 5-200 mass parts. If the inorganic filler is 1 part by mass or more, the effect is exhibited in terms of imparting flame retardancy. On the other hand, if the inorganic filler is 1000 parts by mass or less, mechanical properties such as moldability and strength of the thermoplastic resin composition can be maintained. When an inorganic filler is blended as a non-halogen flame retardant, char (carbonized layer) can be formed and the flame retardancy of a film or the like can be improved.

<Flame Retardant>
Hereinafter, the flame retardant that can be used in the present invention will be described. Examples of the organic flame retardant include, but are not limited to, bromine compounds such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, and aromatics such as triphenyl phosphate. Examples thereof include phosphorus compounds such as phosphoric acid esters of the family, red phosphorus, and phosphoric acid esters containing halogen, nitrogen-containing compounds such as 1,3,5-triazine derivatives, and halogen-containing compounds such as chlorinated paraffin and brominated paraffin.
Examples of the inorganic flame retardant include metal hydroxides such as antimony compounds, aluminum hydroxide, and magnesium hydroxide, which are also the above inorganic fillers.
These flame retardants can be used in an appropriate amount depending on the application. These may be used together with a known appropriate flame retardant aid. Examples of flame retardants are also described in, for example, JP-A No. 11-199724, JP-T 2002-533478, etc. (each of which is incorporated herein by reference).

<Light proofing agent>
The light-proofing agent used in the present invention is a known light-proofing agent. In general, the light-resistant agent is composed of an ultraviolet absorber that converts light energy into harmless heat energy and a hindered amine light stabilizer that traps radicals generated by photooxidation. The mass ratio of the ultraviolet absorber and the hindered amine light stabilizer is preferably in the range of 0: 100 to 100: 1, the total amount of the ultraviolet absorber and the hindered amine light stabilizer is the light-proofing agent mass, and the amount used is Generally, it is preferable that it is the range of 0.05-5 mass parts with respect to 100 mass parts of the thermoplastic resin composition of this invention.

<Other resins>
In the thermoplastic resin composition of the present invention, in addition to the above, 0 to 30 parts by mass of PPE (polyphenylene ether) -based resin as necessary with respect to 100 parts by mass of the thermoplastic resin composition comprising the above-described components. It can be added in a range. By adding in this range, it can be passed on while suppressing the softness of the thermoplastic resin composition from being impaired. By adding a PPE-based resin, it is possible to adjust the hardness and further improve the abrasion resistance with scratches. The PPE resin used is described in WO2009-128444, which is incorporated herein by reference.

<Mixing method>
The method for mixing the cross copolymer, ethylene copolymer, and additive of the present invention is not particularly limited, and a known appropriate blend 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 preferably 150 to 300 ° C, more preferably 200 to 250 ° C.

<Energy beam bridge>
The thermoplastic resin composition of the present invention can be crosslinked using various energy rays. In the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step, the energy ray crosslinkability is improved when the aromatic vinyl compound content is 30 mol% or less, particularly 25 mol% or less, and even at a low dose. There is a feature that a sufficient degree of crosslinking (gel content, heat resistance) can be obtained. This feature is extremely useful because it means that the productivity of the crosslinked sheet is high from an industrial viewpoint. Cross-linking using energy rays is advantageous in that it can be cross-linked after molding. For example, it can be cross-linked while retaining a wrinkle after forming a wrinkled sheet. -Suitable for making sheets and various decorative sheets. Examples of the energy rays used here include particle rays, electromagnetic waves, and combinations thereof. Examples of the particle beam include electron beams (EB) and α rays, and examples of the electromagnetic waves include ultraviolet rays (UV), visible rays, infrared rays, γ rays, and X rays. Among these, an electron beam (EB) is industrially preferable in terms of economical efficiency.

  These energy rays can be irradiated using a known apparatus. In the case of an electron beam (EB), the acceleration voltage is generally 0.1 to 10 MeV, and the irradiation dose is preferably 10 to 500 kGy. This acceleration voltage is appropriately controlled according to the thickness of the sheet. When the entire sheet is to be cross-linked by a single irradiation from the surface, it is necessary that the electron beam is sufficiently transmitted to the back surface of the sheet and the cross-linking proceeds, and at a sheet thickness of 0.25 mm, the acceleration voltage is generally increased. An acceleration voltage of about 500 kV or more is preferably used at 250 kV or more, a sheet thickness of 0.5 mm, and a sheet thickness of 1.0 mm is preferably about 1000 kV or more. Electron beams may be irradiated from both sides of the sheet. For example, at a sheet thickness of 0.5 mm, irradiation from both sides with an acceleration voltage of 250 kV or more enables more reliable crosslinking to the sheet center. In particular, it is preferable to perform crosslinking without using a photopolymerization initiator and a crosslinking aid shown below in view of cost and consideration of these remaining drugs. In that case, by using the cross-copolymer of the present invention, it is possible to perform crosslinking at a low irradiation dose, and productivity is improved. Specifically, when the entire surface including the back surface of the sheet is to be cross-linked by a single irradiation from the front surface, preferably 40 kGy or more, 200 kGy or less, more preferably 50 kGy or more, under the conditions satisfying the above acceleration voltage, Crosslinking can be performed at a low irradiation dose of 150 kGy or less, particularly preferably 50 kGy or more and 100 kGy or less. When cross-linking is performed at an irradiation dose below this upper limit, the possibility of excessive cross-linking can be kept low, the elongation during molding and use can be kept sufficiently, and adhesion to the substrate and other sheets is also possible. It is also possible to suppress the possibility of a decrease.

  When ultraviolet rays (UV) are used as energy rays, a lamp having a radiation wavelength of 200 nm to 450 nm can be suitably used as the radiation source. In addition, a photopolymerization initiator can be further blended in the cross-copolymer of the present invention and its thermoplastic resin composition as required, particularly when ultraviolet rays (UV) are used as energy rays. Usable photopolymerization initiators include, for example, benzophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylol benzoin, α-methylol benzoin methyl ether, α-methoxybenzoin methyl ether, benzoin phenyl ether, α Examples thereof include, but are not limited to, -t-butylbenzoin. These photopolymerization initiators may be used alone or in combination of two or more. When mix | blending a photoinitiator, it is preferable that it is the range of 0.01-5 mass% with respect to the total mass of a copolymer or a resin component.

  A cross-linking aid can be further blended in the cross copolymer and the thermoplastic resin composition of the present invention as required. Crosslinking aids that can be used include, but are not limited to, triallyl isocyanurate, triallyl cyanurate, N, N′-phenylenebismaleimide, ethylene glycol di (meth) acrylate, propanediol di (meth) ) Acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like. These crosslinking aids may be used alone or in combination of two or more. When the crosslinking aid is blended, the content thereof is not particularly limited, but it is usually preferably in the range of 0.01 to 5% by mass with respect to the total mass.

  By blending the photopolymerization initiator or the crosslinking aid, it is possible to crosslink at a lower irradiation dose under the acceleration voltage. In this case, for example, sufficient crosslinking can be performed with an irradiation dose of 10 kGy or more and 100 kGy or less, which is industrially preferable.

The energy beam cross-linked product of the resin composition of the present invention can have improved heat resistance while maintaining the softness inherent in the thermoplastic resin composition. For example, the energy beam cross-linked product has a higher gel content than before cross-linking, preferably 25% by mass or more, particularly preferably 30% by mass or more and 70% by mass or less. When the gel content is at least the lower limit, the heat resistance can be more effectively exhibited. When the gel content is at the upper limit or less, the decrease in the elongation of the crosslinked product can be suppressed and the workability can be maintained. Moreover, the gel content below the upper limit also maintains suitable recyclability, and for example, after adding a certain amount to the recycled material, the possibility of rough skin can be suppressed.
Moreover, in the energy beam cross-linked product, the temperature at which the storage elastic modulus (E ′) is reduced to 3 × 10 ⁵ Pa in the viscoelastic spectrum measurement measured at 1 Hz and the heating rate of 4 ° C./min may be 140 ° C. or higher. it can. The creep start temperature specified in the present specification can be 150 ° C. or higher. When the above heat resistance index is satisfied, the possibility of sheet sagging and deformation particularly during the heat forming process after irradiation with energy rays can be kept low. Moreover, when satisfy | filling the said heat resistant parameter | index, the possibility that the embossing provided before irradiation may lose | disappear at the time of the thermoforming process after irradiation or long-term use as a product can be suppressed low.
The crosslinked energy beam of the resin composition of the present invention has softness as a skin material and good mechanical properties. For example, the initial elastic modulus in a tensile test at 23 ° C. is 1 to 50 MPa, and the elongation at break is 200 to 200. The strength at 1500% and the breaking strength can be in the range of 10-50 MPa.

The energy beam cross-linked product (sheet) of the resin composition of the present invention can also exhibit a value with excellent texture retention according to the following measurement method.
For the texture retention, when the gloss of the energy beam cross-linked product (sheet) is measured and evaluated according to JIS K7105 at an angle of 60 ° light receiving angle of 60 °, the energy beam cross-linked product (sheet) of the present invention is: Even after the heat treatment at 120 ° C. for 120 hours, the gloss is maintained at, for example, an initial value + 5% or less, preferably an initial value + 3% or less.

<Sheet for skin>
The thermoplastic resin composition of the present invention is basically formed into a sheet by a known method and then subjected to a crosslinking treatment with an energy beam (electron beam) to obtain a sheet for a skin material. Although there is no restriction | limiting in particular in the thickness of this sheet | seat for skin materials, 3 micrometers-3 mm are preferable, More preferably, they are 10 micrometers-1 mm.
In order to produce a sheet for skin material composed of the present thermoplastic resin composition, a molding method such as inflation molding, T-die molding, calendar molding, roll molding, or the like can be employed. For the purpose of improving physical properties, the sheet for skin material of the present invention is suitable for other sheet materials such as isotactic or syndiotactic polypropylene, high density polyethylene, low density polyethylene (LDPE or LLDPE). , Polystyrene, polyethylene terephthalate, ethylene-vinyl acetate copolymer (EVA) and other skin material sheets can be multilayered, and multilayered materials are also included in the sheet and skin material sheet of the present invention.

  If necessary, various protective layers may be formed on the synthetic leather or the decorative surface. In particular, it is preferable to form a surface coating material layer of urethane-based resin, acrylic-based resin, or epoxy-based resin by coating or lamination for further improving appearance such as scratch resistance and imparting durability. Preferably, a thermosetting resin such as a two-component curable urethane coating agent or an ionizing radiation curable resin such as an electron beam curable resin is used. This is preferable in that required physical properties such as scratch resistance or other surface physical properties can be easily improved. Also, the ionizing radiation curable resin has a faster curing rate and better productivity than the thermosetting resin. The electron beam curable coating layer is preferable in that it can simultaneously irradiate and crosslink the sheet base material of the present invention below the coating layer.

The sheet of the present invention and the sheet for skin material 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, if necessary. The sheet | seat for skin materials of this invention can be produced as a sheet | seat for extending | stretching skin materials which performed uniaxial or biaxial stretching orientation as needed. The sheet of the present invention and the sheet for the skin material are bonded to each other or a material such as another thermoplastic resin by a method such as fusion by a method such as heat, ultrasonic wave, high frequency, adhesion by a solvent or the like, if necessary. can do.
Although the specific use of the sheet | seat of this invention is not specifically limited, From the outstanding soft property, dynamic physical property, and heat resistance, it is useful as various skin materials. For example, it can be suitably used for synthetic leather, especially synthetic leather for automobile interiors, building materials, and decorative skin materials for home appliances. Although the hardness of this skin material sheet finally obtained is not specifically limited, A hardness is preferably in the range of about 60 to 95. Examples of automotive interior materials include instrument panels, door trims, sheet skins, ceiling materials, floor skins, handles, brakes, levers, grips, and the like. Moreover, it can be used suitably also as a floor mat material. In the case of these uses, it may be used as a multilayer with a polyolefin-based or polyurethane-based foamed sheet, or may be used by foaming itself.

  As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, these Examples do not limit this invention. In addition, unless otherwise indicated, the commercially available reagent mentioned in the Example was used in accordance with the manufacturer's instruction or standard method.

The analysis of the copolymer obtained in the examples was carried out by the following means.
The 13C-NMR spectrum was measured using α-500 manufactured by JEOL Ltd., using deuterated chloroform solvent or deuterated 1,1,2,2-tetrachloroethane solvent and TMS as a reference. The measurement based on TMS here is the following measurement. First, the shift value of the center peak of the triplet 13C-NMR peak of heavy 1,1,2,2-tetrachloroethane was determined based on TMS. Next, the copolymer was dissolved in deuterated 1,1,2,2-tetrachloroethane and 13C-NMR was measured, and each peak shift value was determined as the triplet center peak of deuterated 1,1,2,2-tetrachloroethane. Was calculated on the basis of The shift value of the triplet center peak of deuterated 1,1,2,2-tetrachloroethane was 73.89 ppm. The measurement was performed by dissolving 3% by mass / volume of the polymer in these solvents.
The 13C-NMR spectrum measurement for quantifying the peak area was performed by a proton gate decoupling method in which NOE was eliminated, using a 45 ° pulse with a repetition time of 5 seconds as a standard.

  Determination of the styrene content in the copolymer was carried out by 1H-NMR, and equipment used was α-500 manufactured by JEOL Ltd. and AC-250 manufactured by BRUCKER. It dissolved in deuterated 1,1,2,2-tetrachloroethane, and the measurement was performed at 80 to 100 ° 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 (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene were determined using GPC (gel permeation chromatography). The measurement was performed under the following conditions.
Column: TSK-GEL MultiporeHXL-M φ7.8 × 300 mm (manufactured by Tosoh Corporation) was connected in series.
Column temperature: 40 ° C
Solvent: THF
Liquid feed flow rate: 1.0 ml / min.

  DSC measurement was performed under a nitrogen stream using a DSC200 manufactured by Seiko Denshi. That is, using 10 mg of the resin composition, DSC measurement was performed from −50 ° C. to 240 ° C. at a heating 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.

<Create sample sheet>
As a sample for electron beam irradiation, a sheet having a thickness of 0.25 mm formed by a hot press method (temperature 250 ° C., time 5 minutes, pressure 50 kg / cm ² ) was used. Samples for various tests such as a tensile test and viscoelastic spectrum measurement were obtained by cutting out from a sheet having a thickness of 0.25 mm obtained under the same conditions.

<Electron beam crosslinking>
Using the Iwasaki Electric EB apparatus TYPE: CB250 / 15 / 180L, irradiation with a predetermined irradiation dose (kGy) was performed once at an acceleration voltage of 250 kV.

<Gel content>
The sheet is shredded into 1 mm width and 3 mm length, immersed in toluene at 25 ° C. for 24 hours, further heated at 70 ° C. for 1 h, and then insoluble matter is filtered off with a 100 mesh metal net filter, and its dry weight From this, the toluene-insoluble gel content was calculated as mass%.

<Tensile test>
In accordance with JIS K-6251, the sheet was cut into No. 2 1/2 type test piece shape, and measured using a Shimadzu AGS-100D type tensile tester at a tensile speed of 500 mm / min.

<Viscoelastic spectrum>
A sample for measurement (3 mm × 40 mm) was cut out from the sheet for skin material having a thickness of about 0.25 mm obtained by the above heating press method, and a dynamic viscoelasticity measuring device (Rheometrics RSA-III) was used, with a frequency of 1 Hz, The temperature range was −50 ° C. to + 250 ° C.
Other measurement parameters related to the measurement of the residual elongation (δL) of the sample are as follows.
Measuring frequency 1Hz
Temperature rising rate 4 ° C / min Sample measurement length 10mm
Initial Static Force 5.0g
Auto Tension Sensitivity 1.0g
Max Auto Tension Rate 0.033mm / s
Max Applied Strain 1.5%
Min Allowed Force 1.0g

<Creep start temperature>
A JIS No. 2 small 1/2 dumbbell is suspended in a predetermined oven and heated at a predetermined temperature for 1 hour every 5 ° C in the range from 100 ° C to 170 ° C. Then, the length was measured, and the elongation / shrinkage deformation rate was determined by the following formula. The maximum temperature at which the main elongation / shrinkage deformation rate falls within ± 2% in the longitudinal direction was defined as the heat resistant deformation temperature (creep start temperature).
Elongation deformation rate = 100 × (length after test−length before test) / length shrinkage deformation rate before test = 100 × (length before test−length after test) / length before test <Wrinkle retention test>
An embossed sheet with a thickness of about 0.25 mm was prepared by the above-described hot pressing method using an embossed mold. However, 1 part by mass of a black masterbatch (polyethylene base) was added to each resin used in this test and colored black. The glossiness was measured according to JIS 7105 at an incident angle of 60 ° and a light receiving angle of 60 ° with or without electron beam irradiation under predetermined conditions. After the sheet sample was placed in an oven at 120 ° C. and heat-treated in the atmosphere for 120 hours, the glossiness was measured in the same manner. The results are shown in Table 4.
Gloss was rated as x when it was larger than + 5% relative to the initial value before heat treatment, ◯ when it was larger than the initial value + 5% or less + 3%, and ◎ when it was smaller than the initial value + 3%. The initial value before the heat treatment was about 1% regardless of the resins and resin compositions of the present examples and comparative examples.
<Abrasion resistance test>
Using a sheet with a thickness of 0.25 mm, evaluation was performed by reciprocating wear 3000 times under the condition of No. 6 canvas and weight of 0.5 kg using a Gakushin type friction fastness tester (manufactured by Tester Sangyo Co., Ltd.). It was. If the sheet penetrated due to wear, the number of reciprocating wear until that time was recorded.
Wear mass (mg) = mass before wear test (mg) −mass after wear test (mg)
Visual / tactile sensation ○ Some unevenness is felt by the tactile sensation, and scratches on the surface are visible. × The surface scraping or the dent of the wear surface is obvious, and the surface is rough. Or when the sheet penetrates in less than 3000 round trips.
<Divinylbenzene>
Divinylbenzene is manufactured by Aldrich (purity 80% as divinylbenzene, meta isomer, para isomer mixture, meta isomer: para isomer mass ratio 70:30).

<Catalyst (transition metal compound)>
In Examples 1 to 11 below, rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride (Chemical Formula 3) was used as a catalyst (transition metal compound).

(Synthesis Example 1)
<Production 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 a polymerization polymerization can (autoclave) with a capacity of 50 L, a stirrer and a heating / cooling jacket. Cyclohexane 20.5 kg, styrene 3.2 kg and Nippon Steel Chemical Co., Ltd. divinylbenzene (meta, para-mixed product, purity 81 mass%, divinylbenzene content 61 mmol) were charged, adjusted to an internal temperature of 60 ° C. and stirred (220 rpm) did. Dry nitrogen gas was bubbled into the liquid at a flow rate of 10 L / min for about 30 minutes to purge the water in the system and the polymerization liquid. Next, 50 mmol of triisobutylaluminum and methylalumoxane (manufactured by Tosoh Akzo, MMAO-3A / hexane solution) were added in an amount of 100 mmol (referred to as MAO in the table) based on Al, and the system was purged immediately with ethylene. After fully purging, the internal temperature was raised to 80 ° C., ethylene was introduced, and after stabilization at a pressure of 0.4 MPa (3 kg / cm ² G), from the catalyst tank installed on the autoclave, rac- About 50 ml of a toluene solution in which 100 μmol of dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride and 1 mmol of triisobutylaluminum were dissolved was added to the autoclave. Furthermore, ethylene was supplied through a flow control valve, and polymerization was carried out while maintaining the internal temperature at 85 ° C. and the pressure at 0.4 MPa. The progress of polymerization was monitored from the ethylene flow rate and integrated flow rate. After reaching a predetermined ethylene flow rate, the ethylene supply was stopped, the pressure was released, and the internal temperature was cooled to 70 ° C. (coordination polymerization step). Thereafter, the polymerization liquid was transferred to a heavy can for anionic polymerization having a capacity of 50 L, a stirrer and a heating / cooling jacket. At the same time, several tens ml of the analytical polymerization solution was collected. 260 mmol of n-butyllithium was introduced from the catalyst tank into the polymerization can for anionic polymerization along with nitrogen gas (crossing step). Anion polymerization started immediately, and the internal temperature rose from 70 ° C to 80 ° C temporarily. The temperature was maintained at 70 ° C. for 30 minutes as it was, and stirring was continued to continue polymerization. About 100 ml of methanol was added to the polymerization can to stop anionic polymerization. The obtained polymer solution was poured little by little with a gear pump into vigorously stirred heated water containing a dispersant (pluronic) and potash alum, the solvent was removed, and polymer crumb (size about 1 cm) dispersed in the heated water was added. Obtained. This polymer crumb was centrifuged and dehydrated, air-dried at room temperature for one day and night, and then dried in a vacuum at 60 ° C. until no mass change was observed. The resulting polymer is designated P1.

(Synthesis Examples 2 to 4)
In the same manner as in Synthesis Example 1, polymerization was carried out under the preparation and polymerization conditions shown in Table 1. The obtained polymers are designated as P2 to P4, respectively. .
(Comparative Synthesis Example 1)
As in Synthesis Example 1, except that divinylbenzene was not used, only the coordination polymerization step was carried out under the preparation and polymerization conditions shown in Table 1. In this case, the obtained copolymer is an ethylene-styrene copolymer. The obtained polymer is designated as RP1.

Table 1 shows the polymerization conditions, and Tables 2 to 3 show the compositional analysis values of the obtained cross copolymers and ethylene-styrene copolymers.
Analytical values of the polymer obtained in the coordination polymerization process (polymer yield, composition, molecular weight, etc. in the coordination polymerization process) were measured using a small amount (several tens of ml) of the polymerization solution sampled at the end of the coordination polymerization process. The polymer was precipitated and recovered by mixing and analyzed and analyzed. The divinylbenzene unit content of the polymer obtained in the coordination polymerization step was determined from the difference between the amount of unreacted divinylbenzene in the polymerization solution determined by gas chromatography analysis and the amount of divinylbenzene used for the polymerization.

Moreover, the ratio (mass%) with respect to the cross-copolymer of the copolymer obtained by the coordination polymerization process of a table | surface is the composition of the ethylene-styrene- divinylbenzene copolymer obtained by the coordination polymerization process ( (Styrene content and ethylene content) and the composition of the cross-copolymer obtained through the anionic polymerization process (styrene content and ethylene content) were determined as the amount of change in each composition was due to the mass of cross-chain polystyrene by anionic polymerization. Alternatively, a cross-copolymer is obtained by partially sampling and analyzing the main chain polymer formation mass obtained by sampling and analyzing a part of the polymerization liquid at the end of coordination polymerization and analyzing the polymerization liquid after anionic polymerization. Although this ratio was calculated | required also from the comparison of mass, both values were the values which correspond substantially.

(Examples 1 to 10)
A thermoplastic resin composition was obtained as follows.
Using a Brabender-Plasticorder (PL2000 type manufactured by Brabender), the cross-copolymers (P1 to P4) obtained in Synthesis Examples 1 to 4 and Engage 8100 (Dow Chemical Co., ethylene-1-octene) Polymer, specific gravity 0.87, MFR 200 ° C., 98 N, 10 g / 10 min), antioxidant Irganox 1076 (manufactured by Ciba Specialty Chemicals): 0.1 part by mass, light resistance LA36 (ultraviolet absorber) 0.2 Part by mass, 0.2 part by mass of LA77Y (hindered amine light stabilizer) (both manufactured by ADEKA Corporation) were added, and kneading was performed at 100 rpm at 180 ° C. for 5 minutes.
Using a sheet having a thickness of 0.25 mm molded from the obtained composition by the above-mentioned hot pressing method, electron beam irradiation was carried out under the above-mentioned conditions and at the doses shown in the table. Using the obtained irradiation sheet, a tensile test, a creep start temperature test, and a viscoelastic spectrum measurement were performed. Furthermore, a sheet with a grain having a thickness of about 0.25 mm was prepared from this composition, and a grain holding test was conducted by irradiating with an electron beam in the same manner. The results are shown in Table 4.
However, in Example 5, instead of Engage 8100, EVAFLEX EEA (ethylene-ethyl acrylate copolymer A703) was used. In Example 8, TMPTA (trimethylolpropane triacrylate) was added as a crosslinking aid. In Example 11, polyphenylene ether (PX-100L manufactured by Mitsubishi Engineering Plastics) was added.

(Comparative Examples 1-12)
Comparative Examples 1 and 5 are examples in which the electron beam irradiation was not performed on P1 and P2 obtained in this synthesis example, respectively.
Comparative Examples 2 and 6 are examples in which 50 kGy electron beam irradiation was performed on P1 and P2 obtained in this synthesis example, respectively. Comparative Examples 3 and 7 are examples in which electron beam irradiation was not performed on the same resin compositions as Examples 1 and 2 and Examples 6 and 7, respectively. Comparative Example 8 is an example in which Engage 8100 is blended in an ethylene-styrene copolymer and Engage 8100 is blended in an ethylene-styrene copolymer, and both are irradiated with an electron beam. In Comparative Examples 10, 11, and 12, with respect to the cross-copolymer P1, commercially available PP soft resin (PP / EPR compound), styrene-isoprene hydrogenated block copolymer (SEBS), ethylene-vinyl acetate copolymer It is the example which irradiated the electron beam to the resin composition which mix | blended coalescence (EVA).

The sheet after the electron beam cross-linking of the sheet made of the thermoplastic resin composition of the present invention shown in the examples shows a predetermined gel content, and the temperature at which the storage elastic modulus (E ′) decreases to 3 × 10 ⁵ Pa is shown. It is 140 ° C. or higher, and the creep start temperature is 150 ° C. or higher, indicating that the heat resistance is greatly improved. Glossiness change is also 3% or less, and has high texture retention. Mechanical properties also satisfy the conditions of the present invention.
On the other hand, when the cross copolymer alone is not irradiated with an electron beam, and when irradiated with an electron beam at the same dose as in the examples, the gel content, storage elastic modulus (E ′), creep start temperature, and texture retention are all sufficient. I couldn't get satisfactory results. In the case of the resin composition that does not satisfy the conditions of the present invention (Comparative Examples 8 to 12), the gel content, storage elastic modulus (E ′), and creep start temperature were not satisfactory.

Table 5 shows the results of the abrasion resistance test.
Each sheet of the example did not penetrate through the sheet in the abrasion resistance test, had a relatively small abrasion mass, and the visual / tactile sensation was also “good”. On the other hand, in the sheet | seat which irradiated the electron beam to the Engage 8100 independent goods, the sheet | seat penetrated by abrasion during the test, and it was x determination.
It turns out that the sheet | seat after the electron beam bridge | crosslinking of the sheet | seat which consists of a thermoplastic resin composition of this invention shows high abrasion resistance compared with the sheet | seat only of an ethylene-type copolymer.

  The various embodiments described by the description of the modes for carrying out the invention are not intended to limit the present invention but are disclosed for the purpose of illustration. The technical scope of the present invention is defined by the description of the claims, and those skilled in the art can make various design changes within the technical scope of the invention described in the claims.

  It should be noted that the disclosures of patents, patent applications, and publications cited in this specification are all incorporated herein by reference.

Claims (5)

(1) (i) A copolymerization of an olefin monomer, an aromatic vinyl compound monomer and an aromatic polyene using a single site coordination polymerization catalyst, whereby an aromatic vinyl compound content of 5 mol% or more and 25 mol% or less, A coordination polymerization step of synthesizing an olefin-aromatic vinyl compound-aromatic polyene copolymer having an aromatic polyene content of 0.01 mol% to 0.3 mol%, the balance being an olefin content , and thereafter of (ii) wherein the olefin - aromatic vinyl compound - aromatic polyene copolymer with the coexistence of an aromatic vinyl compound monomer, the more cross-modified to be polymerized with an anionic polymerization initiator or radical polymerization initiator <br/> the polymerization process comprising, olefins obtained by the coordination polymerization step - aromatic vinyl compound - a mass ratio of the aromatic polyene copolymer is 5 A step of producing a cross-copolymer A is 99 wt%,
(2) d styrene content of Ri 60-90% by mass, the ethylene - copolymer and / or ethylene olefin - 80 the ethylene copolymer B is a copolymer of an unsaturated carboxylic acid or its ester A step of cross-linking a thermoplastic resin composition comprising 10 parts by mass and a total of 100 parts by mass of 20 to 90 parts by mass of the cross-copolymer A by energy ray irradiation;
The manufacturing method of the sheet | seat for skin materials characterized by including this . The manufacturing method according to claim 1, wherein the energy beam irradiation is electron beam irradiation. The manufacturing method according to claim 1 or 2, wherein the gel content of the sheet for the skin material is 25% by mass or more and 70% by mass or less. The manufacturing method as described in any one of Claims 1 thru | or 3 whose temperature at which the storage elastic modulus (E ') by the viscoelastic spectrum measurement of the sheet | seat for skin materials falls to 3x10 < ⁵ > Pa is 140 degreeC or more. The manufacturing method as described in any one of Claims 1 thru | or 4 with which the glossiness after heat-processing the sheet | seat for skin materials at 120 degreeC for 120 hours is maintained at + 3% or less compared with the initial value before heat processing.