JP2014189775A - Modified propylenic polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modified propylenic polymer composition capable of suppressing, by abating olefin contents, prospects of molding instabilities attributed to gel formation such as the generation of fish eyes, viscosity gain, etc.SOLUTION: The provided modified propylenic polymer composition includes, as a main component, a terminal-modified propylenic polymer including a modifying group and including a constituent unit expressed by the following (2): (in the formula, Rexpresses a hydrogen atom or aliphatic hydrocarbon group having at least 1 and 4 or fewer carbon atoms); another version of the polymer composition is a modified propylenic polymer composition including, as a main component, a terminal-modified propylenic polymer having a number-average molecular weight of 52,000 or above and 1,000,000 or below wherein the ratio, with respect to all intramolecular modifying groups, of modifying groups coupled with one molecule terminal is 60% or above and 100% or below.

Description

The present invention relates to a modified propylene polymer composition containing a terminal-modified propylene polymer as a main component.
The present invention also relates to a composite resin composition using the modified propylene polymer composition, an adhesive resin composition comprising the composite resin composition, and a laminate including the adhesive resin composition layer.

  Polypropylene, copolymers of propylene and other monomers capable of copolymerization with propylene, and polypropylene-containing resins (hereinafter collectively referred to as “polypropylene resins” or “propylene polymers”), It is inexpensive and has excellent properties such as moldability, heat resistance, water vapor barrier properties, chemical resistance, heat sealing properties, solvent resistance, mechanical properties, and appearance. For this reason, it is processed into various molded products and widely used.

  Depending on the application, the polypropylene resin may be used as a multilayer structure with other types of resins in order to compensate for the drawbacks of the polypropylene resin. For example, in the case of various packaging and container materials, in order to compensate for the disadvantage that the polypropylene resin has poor gas barrier properties against oxygen gas, carbon dioxide gas, etc., content resistance properties such as flavor properties and fragrance retention properties, etc. It is used as a multilayer structure with various other resins such as polyester resin, saponified ethylene-vinyl acetate copolymer, polyamide resin, polycarbonate resin, polystyrene resin and the like.

  However, the polypropylene resin is mainly composed of a saturated hydrocarbon chain having a low polarity, and has poor chemical reactivity with respect to the above-mentioned other types of resins, and therefore has poor adhesion to these resins. Therefore, when such a polypropylene resin has a laminated structure with other types of resins, a resin composition containing a modified polyolefin resin or rubber, a tackifier, a styrene thermoplastic elastomer, etc. is conventionally used between the two resin layers. A method of interposing them as an adhesive layer has been proposed (Patent Document 1).

  As a method for producing the above-mentioned modified polyolefin resin, there has been proposed a method of modifying a polyolefin resin by graft reaction with a carboxylic acid component such as unsaturated carboxylic acid or its anhydride represented by maleic anhydride. For example, this modified polyolefin resin is produced by introducing a carboxylic acid component into a polyolefin chain by a graft reaction using a radical generated by an organic peroxide or a thermal decomposition method in a molten state or a solution state ( Patent Documents 2 to 4).

  Substituents derived from modifiers such as unsaturated carboxylic acids or anhydrides introduced into the polyolefin chain by the modification reaction, that is, the modification groups are bonded mainly by reaction with the above-mentioned other types of resins. Demonstrate adhesion. Therefore, in order to develop the adhesive force due to this reaction, it is preferable that a large number of introduced modified groups are present at sites advantageous for this reaction in the polyolefin chain of the modified polyolefin resin.

JP 2001-98121 A Japanese Patent Laid-Open No. 2002-20436 JP 2003-183336 A JP 2006-328388 A

  The modification reactions described in Patent Documents 1 to 4 use radicals, but as is generally known, the use of peroxides or the like promotes the generation of radicals and initiates / promotes the reaction of olefins. On the other hand, it also causes a side reaction of extracting a hydrogen atom or the like in the polyolefin chain, and induces radicals in the molecular chain with high randomness. As a result, the modifying group introduced into the polyolefin chain is introduced to other than the intended location. At the same time, unnecessary olefin sites are also generated in the polyolefin chain.

  Therefore, when the modified polyolefin resin thus obtained is used for the adhesive layer, the modified group derived from the introduced unsaturated carboxylic acid or its anhydride is present in the polyolefin chain in a highly random form. Therefore, depending on the position of the modifying group, there is a problem that it cannot be effectively involved in the reaction with other types of resins.

  Furthermore, in the resin, composition, and method for producing the same described in Patent Documents 1 to 4, radicals are actively generated in the process of obtaining the modified polyolefin resin, so that an originally unnecessary olefin moiety is generated in the molecular chain. In the obtained resin, composition, and molded product thereof, there was a concern of causing problems such as poor appearance due to the generation of fish eyes caused by gelation. In addition, at the time of molding these modified polyolefin resins, there was also a problem that had concerns such as thickening of the resin due to the reaction of the olefin resin involving radicals.

The present invention has been made in view of the above problems, and optimizes the introduction position of a modifying group derived from a modifying agent such as an unsaturated carboxylic acid or its anhydride into the molecular chain of a propylene-based polymer. Another object of the present invention is to provide a modified propylene-based polymer composition in which the function of the modifying group in the interlaminar adhesion property is further effective.
The present invention also provides a modified propylene polymer composition that reduces the amount of olefin in the molecular chain of the propylene polymer and suppresses concerns about molding instability such as generation of fish eyes and thickening due to the gelation. The purpose is to provide goods.

  As a result of intensive research to solve the above-mentioned problems, the inventors of the present invention have specific conditions such that unnecessary radicals are not generated in the resin production process, have a molecular weight in a specific range, and are specified at the end. By selectively introducing a specific amount of a modifying group into one molecular end of a polypropylene polymer having an amount of olefin groups, it has superior adhesive properties and molding properties compared to conventional fish. It has been found that a modified propylene polymer composition with reduced eye concern can be provided.

  The present invention has been achieved on the basis of such findings, and the gist thereof is as follows.

（式中、Ｒ_１は、変性基を表す。）

（式中、Ｒ_２は、水素原子又は炭素数が１以上４以下の脂肪族炭化水素基を表す。）

[1] It has structural units represented by the following (1) to (3), has a number average molecular weight of 52,000 or more and 1,000,000 or less, and one molecular terminal of all modified groups in one molecule. A modified propylene polymer composition comprising, as a main component, a terminal-modified propylene polymer in which the ratio of the modified group bonded to is from 60% to 100%.

(Wherein R ₁ represents a modifying group)

(In the formula, R ₂ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.)

[2] In [1], the structural units represented by (1) to (3) are directly in the order of (1)-(2)-(3) at the molecular terminals of the terminal-modified propylene polymer. A modified propylene polymer composition characterized by being bonded.

[3] The modified propylene polymer according to [1] or [2], wherein the content of the modified group in the terminal-modified propylene polymer is 0.010 wt% or more and 0.30 wt% or less. Composition.

[4] In any one of [1] to [3], the modifying group is a modifying group derived from one or more modifying agents selected from unsaturated carboxylic acids and their anhydrides and derivatives thereof. A modified propylene-based polymer composition.

[5] In any one of [1] to [4], the terminal-modified propylene polymer is modified with the propylene-based polymer having the structural unit (2) at the terminal in the presence of an antioxidant. A modified propylene polymer composition obtained by reacting with an agent under heating conditions.

[6] A composite resin composition comprising a resin other than the terminal-modified propylene polymer mixed with the modified propylene polymer composition according to any one of [1] to [5].

[7] The composite resin composition according to [6], wherein the content of the modifying group in the composition is 0.015 wt% or more and 0.20 wt% or less.

[8] An adhesive resin composition comprising the composite resin composition according to [6] or [7].

[9] A laminate comprising the adhesive resin composition layer according to [8].

  ADVANTAGE OF THE INVENTION According to this invention, the modified | denatured propylene polymer composition which was excellent in the adhesive characteristic and the shaping | molding characteristic, and reduced concerns, such as gelatinization, can be provided. In particular, the modified propylene-based polymer composition of the present invention is economically advantageous because it exhibits excellent adhesive properties when a smaller amount of modified groups are introduced compared to conventional products. In addition, regarding the adjustment of adhesive strength by changing the concentration of the modifying group in the composition by dilution with other resins, etc., the degree of freedom of adjustment is higher than conventional products, and it is excellent in applicability to a wide range of applications. Yes.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the examples and embodiments described below, and can be arbitrarily changed without departing from the gist of the present invention. Can be implemented.

  In the present invention, a composition containing a specific resin or polymer as a component may be called with the name of the resin or polymer as the main component. Here, the “main component” refers to a component that occupies 50% by weight or more of the composition. That is, the “aliphatic polyester resin composition” refers to a resin composition containing “aliphatic polyester resin” as a main component.

  Further, in this specification, the term “polymer” refers to a polymer composed of a single type of repeating structural unit (so-called “homopolymer”) and a polymer composed of a plurality of types of repeating structural units (so-called “polymer”). It is used as a concept including “copolymer”).

  In the following description, a structural unit (partial structural unit) of a polymer derived from a certain monomer is represented by adding the word “unit” to the name of the monomer. For example, a structural unit derived from dicarboxylic acid is represented by the name “dicarboxylic acid unit”.

  In addition, compounds that give the same structural unit are collectively referred to by a name in which “unit” in the name of the structural unit is replaced with “component”. For example, compounds such as aromatic dicarboxylic acids and aromatic dicarboxylic acid diesters all form aromatic dicarboxylic acid units, even if the reaction in the process of forming the polymer is different. Therefore, these aromatic dicarboxylic acids and aromatic dicarboxylic acid diesters are collectively referred to as “aromatic dicarboxylic acid component”.

In the present invention, in order to modify the propylene polymer, a compound for reacting with the propylene polymer to introduce a substituent for the purpose of imparting a function is referred to as a “modifier”. Thus, the substituent introduced into the propylene polymer is referred to as “modified group”.
In addition, in the laminate of the present invention described later, a layer bonded by an adhesive layer made of the composition of the present invention is referred to as a “bonded layer”.

[1. Terminal-modified propylene polymer]
The terminal-modified propylene polymer (hereinafter referred to as “terminal-modified propylene polymer of the present invention”), which is the main component of the modified propylene polymer composition of the present invention, is represented by the following (1) to (3). The ratio of the modifying group having a structural unit represented, having a number average molecular weight of 52,000 or more and 1,000,000 or less, and bonded to one molecular terminal among all the modifying groups in one molecule is 60 % Or more and 100% or less.

（式中、Ｒ_１は、変性基を表す。）

(Wherein R ₁ represents a modifying group)

（式中、Ｒ_２は、水素原子又は炭素数が１以上４以下の脂肪族炭化水素基を表す。）

(In the formula, R ₂ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.)

[1-1. Constituent unit of terminal-modified propylene polymer]
[1-1-1. Modified group]
[1-1-1-1. Types of modifying groups]
The modifying group represented by the above formula (1) contained in the terminal-modified propylene-based polymer of the present invention (hereinafter sometimes referred to as “modifying group (1)”) originates from the modifying agent and is not modified. The substituent introduced into the propylene-based polymer, the carbon number contained in R ₁ is usually 3 or more, preferably 4 or more, and usually 40 or less, preferably 20 or less, more preferably 10 or less, particularly Preferably it is 5 or less.
If the carbon number of R ₁ is a modifying group within the above range, it is effective for the expression of adhesiveness intended in the present invention.

The modifying agent for introducing such a modifying group (1) is not particularly limited, but generally includes an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a derivative thereof. Specific examples of the saturated carboxylic acid include acrylic acid, methacrylic acid, butenoic acid, crotonic acid, isocrotonic acid, butenoic acid, vinyl acetic acid, pentenoic acid, angelic acid, tibrinic acid, 2-pentenoic acid, 3-pentenoic acid, α -Ethylacrylic acid, β-methylcrotonic acid, 4-pentenoic acid, 2-hexenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoic acid, α-ethylcrotonic acid, 2,2-dimethyl -3-butenoic acid, 2-heptenoic acid, 2-octenoic acid, 4-decenoic acid, 9-undecenoic acid, 10-undecenoic acid, 4-dodecenoic acid, 9-tetradecenoic acid, 9-hexadecec Acid, 2-octadecenoic acid, 9-octadecenoic acid, eicosenoic acid, docosenoic acid, erucic acid, tetracosenoic acid, mycolipenoic acid, 2,4-pentadienoic acid, 2,4-hexadienoic acid, diallylacetic acid, geranium acid, 2,4 -Decadienoic acid, 2,4-dodecadienoic acid, 9,12-hexadecadienoic acid, 9,12-octadecadienoic acid, hexadecatrienoic acid, linoleic acid, linolenic acid, octadecatrienoic acid, eicosadienoic acid, eicosatrienoic acid Enoic acid, eicosatetraenoic acid, ricinoleic acid, eleostearic acid, oleic acid, eicosapetaenoic acid, escinic acid, tocosadenoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid, hexacodienoic acid , Octacosenoic acid, traacontenoic acid, male Acid, dimethyl maleate, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, endo- bicyclo [2.2.2] oct-5-ene -2
, 3-dicarboxylic acid, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid and the like.

  Specific examples of the unsaturated carboxylic acid derivative include methyl ester, ethyl ester, n-propyl ester, i-propyl ester, n-butyl ester, i-propyl ester sec-butyl ester of the above unsaturated carboxylic acid, Examples thereof include esters such as t-butyl ester, hexyl ester, octyl ester, 2-ethylhexyl ester, lauryl ester and stearyl ester, and derivatives such as acid halide, amide and imide.

Further, specific examples of unsaturated carboxylic acid anhydrides include succinic acid 2-octen-1-yl anhydride, succinic acid 2-dodecen-1-yl anhydride, and succinic acid 2-octadecene-1-yl anhydride. Maleic anhydride, 2
, 3-Dimethylmaleic anhydride, bromomaleic anhydride, dichloromaleic anhydride, citraconic anhydride, itaconic anhydride, 1-butene-3,4-dicarboxylic anhydride, 1-cyclopentene-1, 2-dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, exo-3,6-epoxy-1,2,3,6 -Tetrahydrophthalic anhydride, 5-norbornene-2
, 3-dicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, endo-bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic acid anhydride, bicyclo [ 2.2.2] Oct-7-ene-2,3,5,6-tetracarboxylic anhydride and the like.

  These modifiers may be used alone or in combination of two or more in any ratio and combination.

  Among these, as the modifying agent for introducing the modifying group (1), maleic acid, maleic anhydride or a mixture containing these as a main component is preferable. In particular, maleic anhydride is inexpensive and easily available. In addition, the terminal-modified propylene polymer modified with the use of the adhesive layer is preferable because it has high compatibility with the adherend layer and exhibits high adhesiveness as an adhesive resin. That is, the modified group derived from maleic anhydride is bonded to the adherend layer made of a resin having a polar functional group such as a hydroxyl group in the adhesion between the adherend layer and the adherend layer to be bonded in the production of the laminate. And has high adhesion.

[1-1-1-2. Modified group content]
In the terminal modified propylene polymer of the present invention, the content of the modifying group (1) is usually 0.60 or more, preferably 0.70 or more, per molecule of the terminal modified propylene polymer of the present invention. Preferably it is 0.75 or more, more preferably 0.80 or more, particularly preferably 0.85 or more, and usually 1.50 or less, preferably 1.30 or less, more preferably 1.20. Or less, more preferably 1.10 or less, still more preferably 1.00 or less, and particularly preferably 0.95 or less. It is preferable that the number of the modifying groups (1) in one molecule of the terminal-modified propylene polymer is greater than or equal to the above lower limit because the adhesiveness as an adhesive resin is excellent, and is preferably equal to or less than the above upper limit. It is preferable in terms of cost for introduction.

  For the same reason as described above, the content of the modifying group (1) of the terminal-modified propylene polymer of the present invention is usually 0.010 as the weight ratio of the modifying group (1) to the terminal-modified propylene polymer. % By weight, preferably 0.050% by weight or more, more preferably 0.080% by weight or more, more preferably 0.10% by weight or more, still more preferably 0.12% by weight or more, usually 0.30% by weight. Or less, preferably 0.28% by weight or less, more preferably 0.26% by weight or less, more preferably 0.24% by weight or less, still more preferably 0.22% by weight or less, particularly preferably 0.20% by weight or less. It is.

[1-1-1-3. One-end denaturation ratio]
The terminal-modified propylene-based polymer of the present invention is a ratio of the modified group (1) introduced at one molecular terminal out of all the modified groups (1) in one molecule defined by the following formula (hereinafter referred to as “one terminal”). The rate of modification is generally 60% or higher, preferably 70% or higher, more preferably 80% or higher, more preferably 85% or higher, still more preferably 90% or higher, particularly preferably 92% or higher. % Or less.

One-terminal modification ratio = (number of modified groups (1) bonded to one molecular terminal in the molecular chain of the terminal-modified propylene polymer) / {(one molecular terminal in the molecular chain of the terminal-modified propylene polymer) Number of modified groups (1) bonded to the number) + (number of modified groups (1) bonded to other than one molecular end in the molecular chain of the terminal modified propylene polymer) × 100
(That is, for example, when the modifying groups (1) are introduced at both ends of the molecular chain of the terminal-modified propylene polymer, the modifying group bonded to one molecular terminal in the molecular chain of the terminal-modified propylene polymer. The number of (1) is 1, and the number of modified groups bonded to other than the one molecular end in the molecular chain of the terminal-modified propylene polymer is 1, so the one-end modified ratio is 1 / (1 + 1) × 100. = 50%)

  That is, in order to fully exhibit the effect of improving the target adhesive properties and the like in the present invention, a modified group is present only at one molecular terminal (one molecular terminal) of the molecular chain of the terminal modified propylene polymer of the present invention. It is important that (1) is bound. In addition, it is also important that the modifying group (1) is not introduced at other sites in the terminal-modified propylene polymer molecular chain. This is due to the following reason.

The action mechanism in which the terminal-modified propylene-based polymer of the present invention exhibits adhesiveness as an adhesive resin between the adherend layer a and the adherend layer b with poor adhesion to each other is as follows.
Since the terminal-modified propylene polymer of the present invention has a modifying group (1) only at one molecular terminal, the terminal-modifying group (1) can react with the modifying group (1) (reactivity). Due to a strong physical interaction between the adherend layer 1 made of a resin having a substituent) and the modifying group (1) and the reactive substituent, or the modifying group (1) and the reactive substituent, Bond with high adhesive strength. On the other hand, in the polypropylene part having no modifying group (1) (the structural part of the formula (3)), the adhesive layer b made of a resin having no substituent capable of reacting with the modifying group (1) and hydrophobicity Glues by interaction. The terminal-modified propylene polymer of the present invention adheres the adherend layer a and the adherend layer b by such an adhesion mechanism, but not only one molecular terminal of the terminal-modified propylene polymer but the other molecule. When the modifying group (1) is bonded to the terminal or the middle part thereof, the part that is originally intended to exhibit the hydrophobic interaction is attracted and fixed not to the adherend layer b but to the adherend layer a. As a result, the adhesive property between the adherend layer a and the adherend layer b by the terminal-modified propylene-based polymer is not sufficiently exhibited.

  For this reason, the terminal-modified propylene polymer of the present invention is present only at one molecular end in the molecular chain as long as the introduced modifying group (1) is possible, and the modifying group (1) is present at the other site. Is preferably not introduced.

[1-1-1-4. Method for quantifying modified groups]
The content of the modifying group (1) in the terminal-modified propylene polymer of the present invention can be quantified using a known analysis method such as ¹ H-NMR. In this case, the sample preparation conditions and the ¹ H-NMR measurement conditions are not particularly limited as long as the amount of the modifying group (1) can be suitably quantified, but for example, in o-dichlorobenzene-d ₄ solvent. The solution in which the terminal-modified propylene-based polymer of the present invention is dissolved is used as a measurement sample, and quantified by performing ¹ H-NMR measurement at 120 ° C. using a Bruker BioSpin Co., Ltd. “AVANCE III cryo-400 MHz spectrometer”. can do.

Specifically, when the terminal-modified propylene polymer of the present invention is represented by the following formula (I-1) (R ₂ in the formula (2) is a hydrogen atom, maleic acid as the modifying group (1)) The terminal-modified propylene polymer introduced with a substituent derived from an anhydride) is a terminal vinyl-modified propylene polymer described later used as a raw material in the vicinity of 6.15 ppm and 5.35 ppm by ¹ H-NMR measurement. The peak derived from the hydrogen atom of the terminal vinyl group of appears. Moreover, since the peak derived from the hydrogen atom of the double bond part of the position of * 2 in the following formula (I-1) appears in the vicinity of 5.60 ppm and 5.75 ppm, the ratio of these peaks is calculated. Thus, the amount of the terminal modifying group (1) can be determined.

[1-1-1-5. Other modifying groups]
As described above, the modifying group (1) is preferably a modifying group derived from an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a derivative thereof, but as long as the effects of the invention are not significantly impaired, The terminal-modified propylene-based polymer may also contain the following other types of functional groups (hereinafter referred to as “other modified groups (1)”) as a minor component depending on the purpose.

  Specific examples of these other modifying groups (1) include aliphatic or aromatic hydrocarbons such as aldehyde groups, hydroxyl groups, epoxy groups, amino groups, silyl groups, sulfonic acid groups, isocyanate groups, and phenyl carbonate groups. And carbonate groups having the following substituents. Among them, an epoxy group, an isocyanate group, a carbonate group, and the like are bonded layers made of a resin having a polar functional group such as a hydroxyl group in bonding the bonded layer and the bonded layer in the production of a laminate. Is particularly preferred because of its high adhesiveness.

  These other modifying groups (1) can be introduced into the terminal vinyl-modified propylene polymer by a known synthesis method.

  When the terminal-modified propylene polymer of the present invention has these other modified groups (1), the content thereof is usually 0.0001% by weight or more and 0.001% by weight with respect to the terminal-modified propylene polymer. In addition, the total modified group (1) which is usually 0.050% by weight or less, preferably 0.010% by weight or less, including a modified group derived from an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a derivative thereof. ) Is usually 50% by weight or less, preferably 33% by weight or less.

  When the other modifying group (1) is not less than the above lower limit, the effect of improving the adhesiveness and the like due to the introduction of the other modifying group (1) can be sufficiently obtained, and by not more than the above upper limit. In addition, it is possible to sufficiently obtain the excellent adhesive effect inherent in the modification derived from the unsaturated carboxylic acid, the unsaturated carboxylic acid anhydride, or a derivative thereof.

Other modifying groups (1) can also be quantified by the above-mentioned ¹ H-NMR measurement.

[1-1-2. Olefin unit]
The structural unit represented by the formula (2) contained in the terminal-modified propylene polymer of the present invention, that is, the olefin unit (hereinafter referred to as “olefin unit (2)”) has a hydrogen atom or a carbon number of 1. It is a unit having R ₂ which is an aliphatic hydrocarbon group of ˜4. Specific examples of R ₂ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, an i-butyl group, and a t-butyl group. -4 alkyl groups and the like.

  This olefin unit (2) is a propylene polymer having an olefin structure at the molecular terminal described later used as a raw material to be modified when the terminal modified propylene polymer of the present invention is produced (hereinafter referred to as “terminal vinyl modified propylene polymer”). It is a unit derived from the term “polymer”, and is a structural unit formed by the reaction of the modifying agent with the molecular terminal of the terminal vinyl-modified propylene polymer.

The olefin unit (2) is preferably less steric hindrance and lighter in weight around the double bond because of the reactivity of the modifying agent and the modifying group (1). From this viewpoint, R ₂ is a hydrogen atom or methyl. It is preferably a group.

The content of the olefin unit (2) contained in the terminal-modified propylene polymer of the present invention is usually 0.0010 or more, preferably 0.0050 or more per 1000 carbons in one molecule of the terminal-modified propylene polymer. , More preferably 0.010 or more, more preferably 0.050 or more, further preferably 0.10 or more, particularly preferably 0.15 or more, usually 0.50 or less, preferably 0.40. Hereinafter, it is more preferably 0.36 or less, more preferably 0.34 or less, further preferably 0.32 or less, and particularly preferably 0.30 or less.
When the content of the olefin unit (2) is not less than the above lower limit, the reaction rate between the terminal vinyl-modified propylene polymer and the modifier is increased. Safety of kneading and molding by suppressing the generation of olefin sites in the molecular chain in which free radicals generated by heat induction during molding are involved, and branching from the olefin sites and further gelation due to the branching are suppressed. Stability and stability, and quality of manufactured products can be improved.

In the terminal-modified propylene polymer of the present invention, in addition to the olefin unit (2), the hydrogen atom of the olefin bond portion in the formula (2) is a hydrogen atom or a hydrocarbon group having 1 or more carbon atoms, and R ₂ Is contained if the constituent unit represented by the following formula (4) (hereinafter referred to as “olefin unit (4)”) is a trace amount. May be.

（式中、Ｒ_３は、水素原子又は炭素数が１以上の炭化水素基を表す。Ｒ_４は、炭素数が１以上の炭化水素基を表す。）

(In the formula, R ₃ represents a hydrogen atom or a hydrocarbon group having 1 or more carbon atoms. R ₄ represents a hydrocarbon group having 1 or more carbon atoms.)

  Such an olefin unit (4) is a structural unit having a large steric hindrance in the modification reaction and having a heavy weight around the olefin moiety, so that it is less from the viewpoint of easy introduction of the modifying group (1). Preferably, this content is usually 0.010 or less, preferably 0.050 or less, more preferably 0.001 or less per 1000 carbons.

The content of the olefin unit such as the olefin unit (2) contained in the terminal-modified propylene polymer of the present invention can be quantified in the same manner as the content of the modified group (1) described above. Preparation conditions and ¹ H-NMR measurement conditions are not particularly limited as long as the olefin units can be suitably quantified.

Specifically, for example, a substituent derived from maleic anhydride is introduced as the modifying group (1), and R ₂ in the olefin unit (2) is a hydrogen atom, and is represented by the formula (I-1). In the case of the terminal-modified propylene-based polymer, peaks derived from the hydrogen atom at the position of * 2 in the formula (I-1) in ¹ H-NMR measurement appear near 5.60 ppm and 5.75 ppm. From this peak, the amount of the olefin unit (2) can be quantified.

[1-1-3. Propylene unit]
The structural unit represented by the formula (3) contained in the terminal-modified propylene polymer of the present invention, that is, the propylene unit (hereinafter referred to as “propylene unit (3)”) is the terminal-modified propylene-based polymer of the present invention. This is a unit derived from a terminal vinyl-modified propylene-based polymer, which will be described later, used as a raw material to be modified in the production of the polymer, and this propylene unit (3) is the main component of the molecular chain of the terminal-modified propylene-based polymer. Make up part.

The structural unit of the formula (3) is high from the viewpoint of excellent mechanical properties such as heat resistance and viscoelasticity of the terminal-modified propylene polymer of the present invention and the modified propylene-based polymer composition containing the same. It preferably has a structure with stereoregularity, and the mm fraction (isotactic triad fraction (mm)) of three consecutive propylene units obtained by ¹³ C-NMR measurement is usually 90% or more. It is preferable to have the property.

  Here, the mm fraction means that when three consecutive propylene units constituting the polypropylene chain are regarded as one unit, three consecutive propylene units in which the direction of methyl branching in each unit is the same direction. It is a ratio and is a value indicating how much the three-dimensional structure of the methyl group in the molecular chain is controlled isotactically.

  Specifically, three consecutive propylene units can be roughly divided into three types represented by the following formulas (3a) to (3c), but the mm fraction is {number of units of the following formula (3a) } / {Number of units of the following formula (3a) + number of units of the following formula (3b) + number of units of the following formula (3c)} × 100. From the viewpoint of mechanical properties such as heat resistance and viscoelasticity of the polymer and the composition containing it, it is usually more than 90%, preferably 91% or more, more preferably 91.5% or more, and more than 92.0%. More preferably, 92.5% is even more preferable, and 93.0% or more is particularly preferable. Further, the upper limit is usually 100% or less, more preferably 99.8% or less, still more preferably 99.5% or less, still more preferably 99.0% or less, and particularly in terms of product quality control related to industrial costs. From the viewpoint of difficulty, it is preferably 98.5% or less.

The mm fraction of three consecutive propylene units can be calculated using, for example, the result of ¹³ C-NMR measurement under the same conditions as in the case of the olefin unit (2) described above. In this case, sample preparation conditions and ¹³ C-NMR measurement conditions are not particularly limited as long as the propylene unit can be suitably quantified. For example, 2.6 ml of a solvent (o-dichlorobenzene: bromo A solution in which 390 mg of a terminal vinyl-modified propylene polymer molecule having an olefin structure at the molecular end is dissolved in benzene-d ₅ = 8: 2) is used as a measurement sample, and a known spectrometer is used under the following conditions. It can be quantified.
Flip angle: 90 degrees Pulse interval: 15 seconds Resonance frequency: 100 MHz or more Integration count: 128 times or more Observation range: -20 ppm to 179 ppm

For the attribution of the ¹³ C-NMR spectrum, Macromolecules, (1975) 8 pp. 687, Polymer, Vol. 30, p. 1350 (1989), and Japanese Patent Application Laid-Open No. 2009-299045 are helpful. In the following, Japanese Patent Application Laid-Open No. 2009-299045 was particularly referred to.

  Three types of three propylene units constituting a propylene polymer molecule having an olefin structure at the molecular end are represented by the following formulas (3a) to (3c). The following formula (3a) represents the mm structure, the following formula (3b) represents the mr structure, and the following formula (3c) represents the rr structure.

Specifically, the ¹³ C-NMR measurement result used in the mm fraction of the three propylene units is the methyl of central propylene in the three propylene units represented by the following formula (3a) to the following formula (3c). It is the result of having quantified the amount of methyl groups using the carbon peak derived from the group.
The chemical shifts of the three types of methyl groups are as follows.
mm: around 24.3 ppm to 21.1 ppm mr: around 21.2 ppm to 20.5 ppm rr: around 20.5 ppm to 19.8 ppm

  The chemical shift ranges of the three types of methyl groups of interest are generally the above chemical shift ranges. Although it may change slightly depending on the molecular weight or the like, it is easy to identify a signal derived from the focused methyl group.

  Further, as will be described later, this hydrophobic propylene unit (3) contained in the terminal-modified propylene polymer of the present invention is obtained from, for example, a polyolefin resin such as hydrophobic polyethylene or polypropylene, or a resin composition thereof. When the terminal-modified propylene polymer of the present invention or a composition containing the same is bonded to the hydrophobic adherent layer by a hydrophobic interaction with the adherend layer, the propylene unit (3) is used. In order to effectively use the hydrophobic interaction, it is important that no unnecessary substituents are introduced into the propylene unit (3). Therefore, for example, in the modification reaction of the terminal vinyl-modified propylene polymer, the propylene unit (3) is modified with a modifying group (3) using free radicals or radical generators generated by thermal cracking of the propylene unit (3). It is important that 1) etc. are not substantially grafted.

In the molecular chain comprising the propylene unit (3) according to the present invention, if the mm fraction is not less than the above lower limit, a random copolymerization site of mm and mr and / or rr, and / or mm and mr and / or Alternatively, a block copolymerization site with rr may be included.
However, even without having such a complicated three-dimensional structure, the propylene unit (3) described above is excellent only in the desired properties such as adhesion properties, and the terminal-modified propylene polymer to be produced and The mechanical properties such as heat resistance and viscoelasticity of the composition to be contained are excellent, and further, the following [1-1-4. Since it is advantageous for the same reason as described in the section of “Other structural units”, it is usually unnecessary to forcibly introduce the block copolymer site or the random copolymer site.

[1-1-4. Other structural units]
In the terminal-modified propylene-based polymer of the present invention, the polypropylene chain portion composed of the propylene unit (3) has a propylene group, for reasons such as increasing the affinity between the adherend layer and the terminal-modified propylene-based polymer of the present invention. Random copolymerization sites with α-olefins and / or other olefin monomers described below, and / or block copolymerization sites (hereinafter referred to as “block copolymerization sites”) between these α-olefin and / or other olefin monomer-derived polymers and polypropylene. May be referred to as “other polyolefin units”).

  However, the target properties such as adhesive properties are excellent only with the polypropylene chain composed of the propylene unit (3) described above without the block copolymerization site or the random copolymerization site, and the present invention to be produced From the viewpoint of mechanical properties such as heat resistance and viscoelasticity of the terminal-modified propylene-based polymer and the composition containing the same, it is preferable that the above-mentioned other polyolefin units are few or even absent. Furthermore, the production of a polymerized portion having a more complicated structure than that of the propylene unit (3) using a large number of monomers industrially increases the complexity of the equipment and requires many tanks. From the propylene unit (3), there are many industrial disadvantages such as cost, difficulty in stable production management due to the complexity of production reaction, or difficulty in finding the cause of production trouble. The resulting polypropylene chain should be free of the other polyolefin units described above.

  When the other polyolefin unit is introduced into the polypropylene chain composed of the propylene unit (3) for reasons such as increasing the affinity between the adherend layer and the terminal-modified propylene polymer of the present invention, the content is The terminal-modified propylene polymer molecule of the present invention is usually 50% by weight or less, preferably 30% by weight or less, more preferably 10% by weight or less, still more preferably 5.0% by weight or less, 1.0% % By weight or less is further preferred, 0.50% by weight or less is more preferred, 0.10% by weight or less is particularly preferred, and the lower limit is 0% by weight as described above, with 0% by weight being the most preferred amount.

  Examples of the α-olefin include ethylene, 1-butene, 1-hexene, allylcyclopentane, allylcyclohexane, allylbenzene, vinylcyclopropane, and vinylcyclohexane.

  Examples of other olefin monomers include aromatic olefin compounds such as styrene, vinyltoluene, and α-methylstyrene; cyanogenated olefin compounds such as acrylonitrile and methacrylonitrile; ethyl acrylate, propyl acrylate, and n-butyl acrylate. And methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate.

  These may be used alone or in combinations of two or more in any ratio and combination in the production of the terminal vinyl-modified propylene polymer.

[1-2. Molecular structure and physical properties]
[1-2-1. Arrangement of structure / unit]
In the terminal-modified propylene-based polymer of the present invention, the adhesive properties and molding properties are excellent. Compared to conventional products, excellent adhesiveness is exhibited by introducing a substituent (modified group) that expresses a smaller amount of adhesive properties, With regard to the adjustment of the adhesive force performed by changing the concentration of the substituent in the composition by dilution or the like, this book has a higher degree of freedom of adjustment than conventional products and provides an industrially excellent adhesive resin composition. In order to more reliably solve the problems of the invention, the structural units represented by the formulas (1) to (3) contained in the terminal-modified propylene polymer of the present invention are chemically bonded in a specific order. Is preferred.

Specifically, the terminal-modified propylene polymer of the present invention is a molecule having a structure satisfying the following conditions (i) and (ii), that is, the formulas (1) to (3) are terminal-modified propylene. It is preferable that the molecular ends of the system polymer are directly bonded in the order of (1)-(2)-(3).
(I) The structural unit of the above formula (1) is bonded to the right methylene carbon of the above formula (2).
(Ii) The structural unit of the above formula (3) is bonded to the carbon atom to which R ₂ of the above formula (2) is bonded.

  A composition containing a terminal-modified propylene polymer in which the structural unit of the above formula (1), the structural unit of the above formula (2), and the structural unit of the above formula (3) are chemically bonded in the above order is [3-1. Use form] is excellent in adhesion between the adherend layers, and exhibits superior adhesion with the introduction of a smaller amount of the modifying group (1) as compared with the conventional product. Regarding the adjustment of the adhesive force performed by changing the group (1) concentration, the degree of freedom of adjustment is higher than that of the conventional product, and the reason why it is superior is not clear yet, but is presumed as follows.

The structural unit of the above formula (1) at the end of the molecular chain of the terminal-modified propylene polymer of the present invention is the later [3-1. For example, polyester resins and polyester elastomers (hereinafter collectively referred to as “PES resins”), saponified ethylene / vinyl alcohol copolymers (hereinafter referred to as “EVOH”). ), Polyamide-based resins (hereinafter collectively referred to as “PA-based resins”), etc., or adhesive bonds by forming chemical bonds with substituents present in the composition. Is expressed. On the other hand, regarding the structural unit of the formula (2) in the terminal-modified propylene polymer, the hydrophobic structural unit of the formula (3) bonded to the opposite side of the structural unit of the formula (1) is, for example, It is compatible with a polyolefin resin such as polyethylene and polypropylene, or an adherend layer made of the resin composition, and is firmly bonded to the polyolefin resin layer by hydrophobic interaction.
That is, the hydrophobic structural unit of the above formula (3) adheres firmly to the polyolefin resin layer, while the PES resin, EVOH, PA system laminated to improve the properties of the polyolefin resin layer. The adherend layer made of a resin or a resin composition thereof is firmly bonded onto the polyolefin resin layer by being chemically or physically bonded to the structural unit of the above formula (1).

[1-2-2. Number average molecular weight and molecular weight distribution]
The molecular weight of the terminal-modified propylene polymer of the present invention is the number average molecular weight (Mn) obtained by gel permeation chromatography (GPC) measurement described later, in order for the propylene unit (3) to strengthen the hydrophobic bond. In order to obtain an optimum chain length, it is usually 1,000,000 or less, from the viewpoint of lowering melt viscosity and improving processability, 500,000 or less is more preferred, 200,000 or less is more preferred, and 150,000 or less is preferred. More preferably, 100,000 or less is even more preferable, and 80,000 or less is particularly preferable. The lower limit is that the hydrophobic bond is strong and the propylene unit (3) does not escape from the hydrophobic adherend layer. In general, it is 52,000 or more, more preferably 55,000 or more, further preferably 58,000 or more, 00 and particularly preferably equal to or greater than.

  Since the terminal-modified propylene-based polymer of the present invention has an adhesive functional group at the molecular terminal, particularly because its number average molecular weight is relatively large as 52,000 to 1,000,000, mobility is ensured, Since it tends to be unevenly distributed on the bonding surface and has a certain molecular weight, the anchor effect produces a sufficient adhesive force.

  The molecular weight distribution of the terminal-modified propylene polymer of the present invention is usually 4.0 or less, preferably 3.5 or less, and preferably 3.0 or less as a molecular weight distribution (Mw / Mn) obtained by GPC measurement described later. More preferably, it is more preferably 2.8 or less, and particularly preferably 2.5 or less from the viewpoint of a high proportion of the terminal-modified propylene polymer in which the propylene unit (3) has an optimum chain length from the viewpoint of adhesive properties. The lower limit is usually 1.5 or more, more preferably 1.8 or more, further preferably 2.0 or more, and particularly preferably 2.2 or more from the viewpoint of improving the balance between melt fluidity and adhesion processability.

The molecular weight of the terminal-modified propylene polymer molecule of the present invention can be quantified using a known analysis method such as GPC. When measuring by GPC, for example, molecular weight (Mn) and molecular weight distribution (Mw / Mn) can be measured under the following conditions.
Apparatus: GPCV 2000 (2) manufactured by Waters
Detector: RI detector (built-in device)
Column: TSKgel GMH6-HT (7.5 mm ID × 30 cm) (four)
Mobile phase solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 135 ° C
Flow rate: 0.5 ml / min Injection volume: 0.05% by weight × 515.5 μl
Calibration sample: monodisperse polystyrene

  The molecular weight and molecular weight distribution of the terminal-modified propylene polymer of the present invention are almost the same as the molecular weight and molecular weight distribution of the terminal vinyl-modified propylene polymer as a modified raw material before introducing the modifying group (1) with a modifier. Can be considered.

[1-3. Denaturant amount]
The terminal-modified propylene polymer of the present invention obtained by the modification reaction of the terminal vinyl-modified propylene polymer described below may contain an unreacted modifier used for modification.

  The content of the unreacted modifier contained in the terminal-modified propylene-based polymer of the present invention is usually 0% by weight or more, preferably 0.0000010% by weight or more, more preferably 0.0000000050% by weight or more. More preferred is 0.000010% by weight or more, more preferred is 0.000050% by weight or more, still more preferred is 0.00010% by weight or more, particularly preferred is 0.00050% by weight or more, and the upper limit is usually 0.30% by weight. % Or less, preferably 0.20% by weight or less, more preferably 0.10% by weight or less, further preferably 0.010% by weight or less, further preferably 0.0080% by weight or less, and 0.0050% by weight or less. Particularly preferred.

  When the content of the unreacted modifier in the terminal-modified propylene polymer is equal to or more than the above lower limit, it is possible to suppress the manufacturing cost by suppressing the load such as the purification equipment requirements in the purification process. Further, the terminal-modified propylene-based polymer with respect to an unreacted modifier bleed out or an undesired reaction caused by the unreacted modifier, for example, an adherend layer of a laminate, due to being below the above upper limit. It is possible to prevent the unreacted modifier from reacting with the site where the modified group (1) is preferably reacted, and to obtain the original adhesiveness of the terminal-modified propylene polymer.

  In addition, content of the unreacted modifier in the terminal modified propylene polymer of the present invention can be quantified by FT-IR.

[2. Method for producing terminal-modified propylene polymer]
[2-1. reaction]
The terminal-modified propylene-based polymer of the present invention may be produced by any known production method, for example, a melting method, a suspension method and a solution method, a melt kneading method, etc., using any known raw material described later. I can do it.

  In general, the terminal-modified propylene polymer of the present invention is produced by reacting a terminal vinyl-modified propylene polymer, which will be described later, with a modifier under heating conditions. This modification reaction is performed in the presence of a radical generator. It can be carried out under or in the absence of a solvent. In addition, by coexisting an antioxidant, generation of olefin sites in the molecular chain involving free radicals generated by heat induction during the modification reaction, branching from the olefin sites, and further due to the branching It can manufacture, suppressing generation | occurrence | production of performed gelation, and is preferable.

  In the melting method, suspension method and solution method, specifically, the terminal vinyl-modified propylene polymer and a raw material such as a modifier are melted and reacted, or the raw material is suspended or dissolved in the above solvent. It is made to react under the conditions. Alternatively, these raw materials are kneaded and reacted. In any of the production methods, a batch reaction and / or a continuous reaction are usually used. A batch reaction is usually a reaction in which the reaction is carried out batchwise, and a continuous reaction is a method in which the reaction is carried out continuously.

Among these, the method for producing the terminal-modified propylene polymer of the present invention is preferably a solution method capable of providing mild reaction conditions performed in a solvent for the following reasons <1> to <4>.
<1> The reaction rate is fast because the raw materials are dissolved in the reaction system.
<2> Since the terminal vinyl-modified propylene polymer and the modifier react in a diluted state, the reaction between the sites having higher reaction activity occurs more selectively in the reaction system. That is, the reaction between the terminal olefin moiety and the modifying agent is made highly selective, and the modifying group (1) can be introduced into the terminal olefin portion with high selectivity.
<3> Compared with other production methods, free radicals that were thermally induced in the growing molecular chain are impurities other than the raw materials contained in the solvent in the reaction system, such as impurities contained in the solvent itself. The chance of deactivation becomes high and internal olefin sites are less likely to occur.
<4> Since heat-induced free radicals are easily deactivated for the same reason as <3>, the occurrence of branching and gelation caused by subsequent reactions caused by the free radicals can be suppressed.

  In particular, when an antioxidant is present, the internal olefin moiety, the branched moiety, and the gelation moiety described in the above <3> and <4> contained in the produced terminal-modified propylene polymer. Can be effectively suppressed.

  Furthermore, as long as the effects of the present invention are not significantly impaired, it is possible to promote the reaction using a radical generator. However, while the radical generator promotes the reaction, the above internal olefin moiety, Since the generation of the site and the gelled site is also promoted, as described later, when the melting method, the suspension method and the solution method are employed, it is preferable to reduce the amount used or not to use as much as possible.

  In addition, the terminal-modified propylene polymer of the present invention is an impurity contained in the crude terminal-modified propylene polymer obtained by the above reaction, for example, unreacted as long as the composition of the present invention is obtained by containing it. In order to remove raw materials, unreacted denaturing agents and by-products, any known separation / purification method, for example, reprecipitation method, extraction method represented by liquid-liquid extraction or solid-liquid extraction, separation by molecular size And a separation / purification method such as a separation method using an ion exchange resin, a filter separation method, and the like, whereby a highly purified terminal-modified propylene polymer can be obtained.

  The terminal-modified propylene polymer of the present invention may be derived from biomass resources. There is no restriction | limiting in the kind of biomass resource, or its manufacturing method, unless the effect of this invention is impaired remarkably. For example, biomass resources obtained by induction to a carbon source through any known pretreatment / saccharification process such as chemical treatment of acids and alkalis, biological treatment using microorganisms, and physical treatment Can also be used.

  Hereinafter, the case where the terminal-modified propylene polymer of the present invention is produced by a batch type solution method will be described in detail, but the procedure of the production method is not limited to this, and some steps are omitted. However, it may be changed to another process, or another arbitrary process may be added. Further, the production method of the terminal-modified propylene polymer of the present invention is not limited to the batch solution method as mentioned above.

[2-2. material]
[2-2-1. Denaturant]
Specifically, the modifier used in the method for producing a terminal-modified propylene polymer of the present invention is [1-1-1. In the section of “Modifying group”, those mentioned as the modifying agent for introducing the modifying group (1) may be used alone, or these modifying agents may be used alone or in any ratio of two or more. You may use together in combination.

[2-2-2. Terminal vinyl-modified propylene polymer]
[2-2-1. Olefin content of terminal vinyl-modified propylene polymer]
The terminal vinyl-modified propylene polymer, which is a raw material to be used for the production of the terminal-modified propylene polymer of the present invention, is preferably propylene containing a terminal olefin structure represented by the following formula (15) in a high proportion. Based polymer. This terminal olefin structure is preferably introduced to the end of the propylene polymer without using a thermal decomposition method for reasons such as ease of molecular weight control and improvement of the purity of the terminal olefin.
For example, the resin provided in the invention described in Japanese Patent Application Laid-Open No. 2009-299045 can be modified by appropriately controlling the terminal vinyl-modified propylene-based polymer of the raw material to be modified by appropriately controlling the molecular weight and molecular weight distribution so as to exhibit the effects of the present invention. It can be suitably used as a coalescence.

（式中、Ｒ_２は、前記式（２）のＲ_２と同義であり、水素又は炭素数が１〜４の脂肪族炭化水素基を表す。）

(Wherein, _{R 2} has the same meaning as _{R 2} in the formula (2), hydrogen or carbon atoms represent 1-4 aliphatic hydrocarbon group.)

  The terminal vinyl-modified propylene-based polymer has an olefin structure represented by the following formula (6) at substantially one terminal present in the molecular chain. By reacting the terminal olefin moiety with the modifying agent, the terminal modified propylene polymer of the present invention in which the modifying group (1) is introduced at one terminal is produced.

（式中、Ｒ_２は、前記式（２）のＲ_２と同義であり、水素又は炭素数が１〜４の脂肪族炭化水素基を表す。）

(Wherein, _{R 2} has the same meaning as _{R 2} in the formula (2), hydrogen or carbon atoms represent 1-4 aliphatic hydrocarbon group.)

  Further, the propylene main chain of the terminal vinyl-modified propylene polymer molecule becomes a structural unit of the above formula (3), and this structural part is a polyolefin such as polyethylene or polypropylene mainly at the time of production or formation of a laminate. It dissolves in an adherend layer made of a resin or a resin composition thereof and exhibits strong adhesiveness due to a hydrophobic interaction with the adherend layer.

Reactivity between the terminal olefin moiety of the terminal vinyl-modified propylene polymer represented by the above formula (15) and the modifier, and adhesion of the modified group (1) introduced at one end of the terminal-modified propylene polymer molecule. From the viewpoint of reactivity, it is preferable that the steric hindrance around the terminal olefin moiety is small and the weight of the terminal olefin moiety is light, that is, R ₂ is a hydrogen atom or a methyl group. That is, the above formula (6) is preferably represented by the following formula (7) or the following formula (8).

The terminal vinyl-modified propylene polymer when R ₂ is a hydrogen atom is shown in the following formula (16), and the terminal vinyl-modified propylene polymer when R ₂ is a methyl group is shown in the following formula (17).

  Only one terminal of the terminal vinyl-modified propylene polymer as a raw material is modified to an olefin structure represented by the above formula (6), preferably the above formula (7) and / or the above formula (8). Preferably, the terminal vinyl modification ratio of the terminal vinyl-modified propylene-based polymer is expressed as {the above formula (6), preferably the number of terminal olefin groups represented by the above formula (7) and / or the above formula (8). } / {Number of molecular chains} × 100, this ratio is usually 60% or more, preferably 65% or more, more preferably 70% or more, and further preferably 72% or more. 75% or more is particularly preferable because the polymer can be produced efficiently. Also. The upper limit of the terminal vinyl modification ratio is usually 150% or less, preferably 110% or less, more preferably 105% or less, more preferably 100% or less, and even more preferably 98% or less. From the viewpoint of ease, it is particularly preferably 95% or less. In addition, as for the numerical value% part exceeding 100% as the upper limit (%) of the terminal vinyl modification ratio, both ends of the terminal vinyl-modified propylene polymer are represented by the above formula (6), preferably the above formula (7) and / or It indicates that the olefin structure represented by the above formula (8) has been modified. Therefore, this value is preferably 100% or less.

Here, the number of terminal olefin groups represented by the above formula (6), preferably the above formula (7) and / or the above formula (8) is calculated by quantitative analysis using ¹³ C-NMR described below. can do. The number of molecular chains is [2-2-2-2. The number average molecular weight and molecular weight distribution] can be calculated from the number average molecular weight obtained by the quantitative analysis using GPC described in the section.

  When the terminal olefin group is represented by the above formula (6), preferably the above formula (7) and / or the above formula (8), a vinyl group per 1000 carbons in one molecule of the terminal vinyl-modified propylene polymer. The total number is usually 0.0050 or more, preferably 0.010 or more, more preferably 0.050 or more, still more preferably 0.010 or more, because of the reaction rate between the vinyl group and the modifier. Particularly preferably, it is 0.012 or more, and it is usually 0.40 or less, preferably 0.35, because side reactions such as reaction between terminal vinyl-modified propylene polymers can be suppressed. Hereinafter, it is more preferably 0.30 or less, more preferably 0.25 or less, further preferably 0.23 or less, and particularly preferably 0.20 or less.

  In addition, in the terminal vinyl-modified propylene polymer, which is a raw material to be modified, the propylene polymer represented by the following formula (18) having a terminal olefin group represented by the following formula (9) is used in a small amount. May be included.

（式中、Ｒ_３は、前記式（４）におけると動議であり、水素原子又は炭素数が１以上の炭化水素基を表す。Ｒ_４は、前記式（４）におけると動議であり、炭素数が１以上の炭化水素基を表す。）

(Wherein R ₃ is a motion in the formula (4) and represents a hydrogen atom or a hydrocarbon group having 1 or more carbon atoms. R ₄ is a motion in the formula (4), Represents a hydrocarbon group having a number of 1 or more.)

However, since both R ₃ and R ₄ are bulky and heavy substituents, the reactivity of the terminal olefin group described above is reduced, and the modified group (1) introduced into the terminal olefin site is also described above. From the viewpoint of reducing the reactivity, the total amount of terminal olefin groups represented by the above formula (9) is usually less than 0.010 per 1000 carbons of all terminal vinyl-modified propylene polymers, more preferably 0.0050. Hereinafter, from the viewpoint of easy introduction of the modifying group (1), it is preferably 0.001 or less, and particularly in the terminal vinyl-modified propylene-based polymer, the propylene-based polymer represented by the above formula (18). It is preferable not to contain a polymer.

Here, the number of terminal olefin groups represented by the above formulas (6) to (9) per 1000 carbons in one molecule is calculated using the quantitative analysis results using ¹³ C-NMR described below. be able to.
That is, the amount of the terminal olefin group represented by the above formulas (6) to (9) can be measured, for example, in the same manner as in the case of the quantitative determination of the modifying group (1). In this case, the sample preparation conditions and the ¹³ C-NMR measurement conditions are not particularly limited as long as the terminal olefin group can be suitably quantified. For example, 2.6 ml of a solvent (o-dichlorobenzene: A solution obtained by dissolving 390 mg of a terminal vinyl-modified propylene polymer in bromobenzene-d ₅ = 8: 2) is used as a measurement sample, and can be quantified under the following conditions using a known spectrometer.
Flip angle: 90 degrees Pulse interval: 15 seconds Resonance frequency: 100 MHz or more Integration count: 128 times or more Observation range: -20 ppm to 179 ppm

Specifically, for example, the amounts of terminal olefin groups of the terminal vinyl-modified propylene polymer represented by the following formula (16) are * 3 and * 4 in the following formula (16) in ¹³ C-NMR measurement, respectively. Peaks derived from the carbon atoms at the positions appear at around 111.2 ppm and around 144.5 ppm, and can be determined by quantifying these peaks.
In addition, for example, the terminal olefin group amount of the terminal vinyl-modified propylene polymer represented by the following formula (17) has peaks derived from carbon atoms at positions * 5 and * 6 in the following formula (17), respectively. , Appearing near 115.5 ppm and 137.6 ppm, it can be determined by quantifying this peak.

[2-2-2-2. Number average molecular weight and molecular weight distribution]
The propylene main chain of the terminal vinyl-modified propylene polymer molecule used as the raw material to be modified is composed of the above formula (3), and this structural portion forms the multilayer structure of the laminate of the present invention. In addition, it is compatible with an adherend layer composed of a polyolefin resin such as polyethylene or polypropylene, or a resin composition thereof, and exhibits strong adhesiveness due to hydrophobic interaction with the adherend layer.
Therefore, the chain length of the unit of the formula (3), in a broad sense, the chain length of the terminal vinyl-modified propylene polymer has an important relationship with the adhesiveness of the composition of the present invention.

  The molecular weight of this terminal vinyl-modified propylene-based polymer is the number average molecular weight (Mn) obtained by GPC measurement described later, and the optimal chain length for the propylene main chain of formula (3) to strengthen the hydrophobic bond. Therefore, it is usually 1,000,000 or less, and from the viewpoint of lowering the melt viscosity and improving workability, 500,000 or less is more preferable, 200,000 or less is more preferable, and 150,000 or less is more preferable. 100,000 or less is even more preferable, and 80,000 or less is particularly preferable. The lower limit is that the hydrophobic bond is strong and the propylene main chain of the formula (3) does not escape from the hydrophobic adherend layer. Therefore, usually 55,000 or more and 58,000 or more are more preferable, and 60,000 or more are more preferable.

  Further, the molecular weight distribution of the terminal vinyl-modified propylene polymer is usually 4.0 or less, more preferably 3.5 or less, and more preferably 3.0 or less, as a molecular weight distribution (Mw / Mn) obtained by GPC measurement described later. Is more preferably 2.8 or less, and from the viewpoint of a high ratio of the terminal vinyl-modified propylene polymer in which the propylene main chain composed of the formula (3) has an optimum chain length from the viewpoint of adhesive properties is 2.5. The following is particularly preferable, and the lower limit thereof is usually 1.5 or more, more preferably 1.8 or more, further preferably 2.0 or more, and particularly preferably 2.2 or more from the viewpoint of improving the melt fluidity.

  The molecular weight of the terminal vinyl-modified propylene polymer can be quantified using a known analysis method such as GPC. When measuring by GPC, for example, molecular weight (Mn) and molecular weight distribution (Mw / Mn) can be measured under the following conditions.

Equipment: GPC manufactured by Waters (ALC / GPC, 150C)
Detector: MIRAN, 1A, IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml
Calibration sample: monodisperse polystyrene

[2-2-2-3. Structural properties of polypropylene chains]
In the production of the terminal-modified propylene polymer of the present invention, the terminal vinyl-modified propylene polymer having an olefin structure at the molecular terminal used as the raw material to be modified is the above-mentioned terminal-modified propylene polymer produced by using the above-mentioned terminal-modified propylene polymer. Any propylene-based polymer having an olefin structure at any known molecular end may be used as long as it satisfies the respective conditions and the composition of the present invention containing the same exhibits the effects of the present invention, and is not particularly limited. .

Such propylene-based polymer molecules are, for example, specifically those having excellent mechanical properties such as heat resistance and viscoelasticity of the terminal-modified propylene-based polymer to be produced and the composition of the present invention containing the same. In view of the above, a propylene-based polymer molecule having a high stereospecific structural characteristic is preferable. For example, it is preferable that the mm fraction of three consecutive propylene units obtained by ¹³ C-NMR usually has a high stereoregularity of 90% or more.

  From the viewpoint of mechanical properties such as heat resistance and viscoelasticity of the terminal-modified propylene polymer to be produced and the composition of the present invention containing the same, the mm fraction of this propylene polymer is usually 90% or more, 91% or more is preferable, 91.5% or more is more preferable, 92.0% is further more preferable, 92.5% is further more preferable, and 93.0% or more is particularly preferable. Further, the upper limit is usually 100% or less, preferably 99.8%, more preferably 99.5%, further preferably 99.0%, particularly in terms of the difficulty in product quality control related to industrial costs. To 98.5% or less is preferable.

Here, the mm fraction of three consecutive propylene units is [1-1-3. It can be calculated by using the results obtained by ¹³ C-NMR measurement under the same conditions detailed in the section “Propylene unit”. In this case, the sample preparation conditions and the ¹³ C-NMR measurement conditions are not particularly limited as long as the propylene unit can be suitably quantified.

The structure of mm of three consecutive propylene units is the same as that in the above formula (3a), the structure of mr is the same as that in the above formula (3b), and the structure of rr is the same as that in the above formula (3c). ^{In 13} C-NMR measurement, [1-1-3. In the same manner as described in the section of “propylene unit”, the amount of methyl group is determined using the peak of the carbon atom derived from the methyl group of the central propylene in the three consecutive propylene units represented by the formulas (3a) to (3c). Quantify.
The chemical shift of the three types of methyl groups is [1-1-3. The same as in the section “Propylene unit”. The chemical shift range of the above-mentioned three types of methyl groups of interest is generally the ft range in the above chemical scheme. Although it may change slightly depending on the molecular weight or the like, it is easy to identify a signal derived from the focused methyl group.
As described above, the propylene polymer having an olefin structure at the molecular end, which is a raw material to be modified in the production of the terminal-modified propylene polymer of the present invention, may be derived from biomass resources.

[2-2-2-4. Other polyolefin units]
The terminal vinyl-modified propylene polymer, which is a raw material to be modified, used in the production of the terminal-modified propylene polymer of the present invention is [1-1-4. Other polyolefin units of the types and ratios detailed in the section “Other structural units” may be contained in the propylene chain portion, but as described above, it is preferable that no other polyolefin units exist.

[2-2-3. solvent]
In the production of the terminal-modified propylene polymer of the present invention, any known solvent can be used as the solvent used in the suspension method and the solution method as long as the production reaction of the terminal-modified propylene polymer is not inhibited.

  Specific examples thereof include aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, and tetradecane; alicyclic hydrocarbons such as methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, and cyclododecane; benzene, toluene, Aromatic hydrocarbons such as xylene, ethylbenzene, cumene, ethyltoluene, trimethylbenzene, cymene, diisopropylbenzene; halogenated carbonization such as chlorobenzene, bromobenzene, o-dichlorobenzene, carbon tetrachloride, trichloroethane, trichloroethylene, tetrachloroethane, tetrachloroethylene Hydrogen; and the like. These solvents may be used alone or in combination of two or more in any combination and ratio.

  Among these, toluene, xylene, and o-dichlorobenzene are highly compatible with the terminal-modified propylene polymer grown in the heating reaction system. For example, the reaction system before the addition of the solvent and the solvent are separated. Among these, o-dichlorobenzene is preferable because it does not disturb the reaction system such as non-uniformity, and is particularly preferable because of its high compatibility at high temperatures.

[2-2-4. Antioxidant]
When producing the terminal-modified propylene-based polymer of the present invention, it is preferable that an antioxidant exemplified below is allowed to coexist in the reaction system for the following reasons.

  In the production reaction of the terminal-modified propylene polymer, that is, in the modification reaction of the terminal vinyl-modified propylene polymer described above, the raw material and the growth polymer molecule are under heating conditions. At this time, for example, radicals are generated by thermally induced growth molecular chain scission or by heat-induced extraction of hydrogen atoms in the molecular chain, and it is common for this to generate olefins in the molecular chain. Well known.

  Further, by reducing the molecular weight by cutting the molecular chain, it is impossible to produce a terminal-modified propylene-based polymer having a molecular weight that exhibits sufficient mechanical properties; Problems such as generation of eyes; gelled products that grow greatly in the reaction tank are generated, resulting in manufacturing troubles and difficult manufacturing management. Therefore, it is very important to carry out the reaction while suppressing the decrease in molecular weight and increase in the amount of olefin.

  As a result of intensive studies to solve the above problems, the present inventors have introduced a specific amount of a specific antioxidant into the production process as described below, thereby reducing the molecular weight and gelation as described above. It has been found that various problems caused by the problem can be sufficiently suppressed.

  The timing of introducing the antioxidant into the reaction system when producing the terminal-modified propylene polymer is not particularly limited as long as the above-described effect of introducing the antioxidant is expressed, and it can be introduced at any modification reaction timing. Good. Specifically, an arbitrary time from the start of the denaturation reaction, from the start of the denaturation reaction to just before the end of the denaturation reaction can be raised. Here, “immediately before the end” indicates 3 minutes before the end of the reaction.

  As an example of the best introduction method in which the effect of the antioxidant lasts from the start to the end of the production of the terminal-modified propylene polymer, three times before the start of the modification reaction, at the middle point of the modification reaction, and immediately before the end of the modification reaction. A method of introducing an antioxidant at a time is mentioned.

  The antioxidant can be introduced in any form into the reaction system for producing the terminal-modified propylene polymer. For example, it may be introduced in a solid (powder) state, as a solution dissolved in a solvent, or as a slurry dispersed in a solvent. The number of introductions may be performed once in any of the above introduction periods, or may be introduced in two or more times. In the case of introducing in a plurality of times, it may be introduced so that the effect of the antioxidant is effectively expressed in the reaction system. The introduction amounts at the time of introduction may be equal or not equal.

  The method of introduction is not particularly limited as long as it can be smoothly introduced without degrading the quality of the antioxidant. For example, when it is introduced in a solid state, it is provided between the antioxidant storage tank and the reaction tank. And a method of introducing the antioxidant into the reaction tank from the antioxidant supply line. On the other hand, when introducing as a solution dissolved in a solvent or as a slurry dispersed in a solvent, for example, a method of installing a mixing tank of a solvent and an antioxidant and stirring with a stirring blade, and / or A line that allows the slurry to flow from the lower part to the upper part is provided, and a uniform solution or slurry is prepared by a vertical circulation method or the like that sucks up the slurry from the lower part to the upper part with a pump or the like and throws it into the mixing tank from the upper part of the mixing tank. Thereafter, a method of feeding by a pump from a supply line provided between the mixing vessel and the reaction vessel with a pump, a method of introducing pressure with an inert gas such as nitrogen, or the like can be given. In the case of introducing the antioxidant as a slurry, the property of the slurry is preferably a property in which the antioxidant particles are stably dispersed in the slurry and hardly settled. Therefore, in addition to stirring as described above, it is preferable to increase the slurry viscosity by setting the antioxidant concentration of the slurry to a high concentration of 5% by weight or more.

  Here, the solvent means the above [2-2-3. Those described in detail in the section of [Solvent] can be used, and the effect of the antioxidant is not significantly impaired, and the solubility of the antioxidant is good, or the dispersion stability of the antioxidant is high and the fluidity is good. Any slurry can be used as long as the slurry properties can be maintained and the production reaction of the terminal-modified propylene polymer is not inhibited.

  Among the aforementioned solvents, toluene, xylene, and o-dichlorobenzene are highly compatible with the terminal-modified propylene polymer grown in the heating reaction system. For example, the reaction system before the addition of the solvent and the solvent Is preferable because it does not disturb the reaction system such as phase separation and heterogeneity, and o-dichlorobenzene is particularly preferable because of its high compatibility at high temperatures.

  A solvent may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  Any antioxidant can be used as long as the effects of the present invention are not significantly impaired. Specific examples thereof include dibutylhydroxytoluene (BHT; 2,6-dibutyl-4-methylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pentaerythritol tetrakis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxy) benzene, 3, , 3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) Tyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, calcium diethylbis [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate Bis (2,2′-dihydroxy-3,3′-di-tert-butyl-5,5′-dimethylphenyl) ethane, N, N′-hexane-1,6-diylbis [3- (3,5 Hindered phenolic antioxidants such as di-tert-butyl-4-hydroxyphenylpropionamide; tridecyl phosphite, diphenyldecyl phosphite, tetrakis (2,4-di-tert Butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid, bis Phosphorous antioxidants such as (2,4-di-tert-butylphenyl) pentaerythritol diphosphite; reactive organisms of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and xylene Lactone-based antioxidants such as dilauryl thiodipropionate, sulfur-based antioxidants such as distearyl thiodipropionate; and the like.

  An antioxidant may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Among these, since it is easily available, inexpensive, and highly effective, it is a hindered phenol antioxidant dibutylhydroxytoluene (BHT; 2,6-dibutyl-4-methylphenol), pentaerythritol tetrakis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxy) Benzene is preferred, and since the produced resin is less colored, dibutylhydroxytoluene (BHT; 2,6-dibutyl-4-methylphenol), pentaerythritol tetrakis [3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate] is more preferred, (3,5-di-tert-butyl 4-hydroxyphenyl) propionate] (e.g. Irganox1010 manufactured by Ciba Japan KK) are inexpensive, particularly preferred since it is easy to use.

  Further, the total amount of the antioxidant introduced is usually 0.00010% by weight or more, based on the total weight of the terminal vinyl-modified propylene-based polymer and the modifier, which are raw materials to be introduced into the reaction tank, and is 0.0. 0010% by weight or more is preferred, 0.010% by weight or more is more preferred, 0.10% by weight or more is more preferred, 0.30% by weight or more is even more preferred, and 0.40% by weight or more is particularly preferred. The upper limit is usually 30.0% by weight or less, more preferably 20.0% by weight or less, still more preferably 15.0% by weight or less, and particularly preferably 12.0% by weight or less. When the introduction amount of the antioxidant is equal to or more than the above lower limit, the effect of the antioxidant can be effectively obtained, and when it is equal to or less than the above upper limit, the manufacturing cost is suppressed and the antioxidant is bleed out. Can be prevented. In addition, when using together 2 or more types of antioxidant, it is preferable that the total of those usage-amounts satisfy | fill the said range.

[2-2-5. Phosphorus heat stabilizer]
When producing the terminal-modified propylene polymer of the present invention, it is preferable that a phosphorous heat stabilizer exemplified below is allowed to coexist in the reaction system for the following reasons.

  As described above, during the production reaction of the terminal-modified propylene polymer, the raw material is under heating conditions. At this time, in order to produce a terminal-modified propylene-based polymer having a desired molecular weight, it is important to produce the terminal-modified propylene polymer while sufficiently suppressing the molecular weight reduction by thermally induced growth molecular chain scission. This is because, as described above, a terminal-modified propylene polymer having a molecular weight that exhibits sufficient mechanical properties due to the low molecular weight cannot be produced.

  In the production process, by mixing the following phosphorous heat stabilizer into the reaction system, thermal stabilization of the terminal-modified propylene polymer growing in the reaction tank is expressed, and the terminal-modified propylene polymer at high temperature Manufacture is possible.

  Moreover, it is preferable to introduce | transduce a phosphorus thermal stabilizer into a reaction tank with an antioxidant simultaneously for the reason of the ease of operation. In this case, the phosphorus-based heat stabilizer and the antioxidant may be mixed and introduced using an antioxidant addition line directly connected to the reaction tank, or may be introduced separately. Moreover, you may install from the introduction line for exclusive use of a phosphorus thermal stabilizer different from the antioxidant addition line directly connected to a reaction tank, and to introduce from there.

  The timing of introducing the phosphorus-based heat stabilizer into the reaction system for producing the terminal-modified propylene-based polymer is not particularly limited as long as the above-described effect of introducing the phosphorus-based heat stabilizer is manifested, and it is introduced at any modification reaction timing. May be. Specific examples include any time before the start of the denaturation reaction and after the start of the denaturation reaction until just before the end. Here, “immediately before the end” indicates 3 minutes before the end of the reaction.

  As an example of the best introduction method in which the effect of the phosphorus-based heat stabilizer lasts from the start to the end of the production of the terminal-modified propylene-based polymer, 3 The method of introduce | transducing a phosphorus-type heat stabilizer in the time of a round is mentioned.

  The phosphorus heat stabilizer can be introduced in any form into the reaction system for producing the terminal-modified propylene polymer. For example, it may be introduced in a solid (powder) state, as a solution dissolved in a solvent, or as a slurry dispersed in a solvent. The number of introductions may be performed once in any of the above introduction periods, or may be introduced in two or more times. In the case of introducing in a plurality of times, it may be introduced so that the effect of the phosphorus heat stabilizer is effectively expressed in the reaction system. The introduction amounts at the time of introduction may be equal or not equal.

  The introduction method is not particularly limited as long as it can be smoothly introduced without degrading the quality of the phosphorous heat stabilizer, but for example, when introduced in a solid state, the reaction is performed from the storage tank of the phosphorous heat stabilizer. The method etc. which introduce | transduce into a reaction tank from the phosphorus thermal stabilizer supply line provided between tanks are mentioned. On the other hand, when introducing as a solution dissolved in a solvent or as a slurry dispersed in a solvent, for example, a method of installing a mixing tank of a solvent and a phosphorus heat stabilizer and stirring with a stirring blade, and / or mixing Provide a line through which the slurry can flow from the lower part to the upper part of the tank, suck up the slurry from the lower part to the upper part with a pump, etc., and throw it into the mixing tank from the upper part of the mixing tank. After the preparation, a method of feeding by pumping into a reaction tank from a supply line provided between the mixing tank and the reaction tank, a method of introducing pressure by an inert gas such as nitrogen, or the like can be mentioned. When the phosphorus-based heat stabilizer is introduced as a slurry, it is preferable that the properties of the slurry are such that the phosphorus-based heat stabilizer particles are stably dispersed in the slurry and hardly settled. Therefore, in addition to stirring as described above, it is preferable to increase the slurry viscosity by setting the concentration of the phosphorus-based heat stabilizer in the slurry to a high concentration of 5% by weight or more.

  Here, the solvent means the above [2-2-3. Those described in detail in the section of “Solvent” can be used, and the effect of the phosphorus-based heat stabilizer is not significantly impaired, and the solubility of the phosphorus-based heat stabilizer is good, or the dispersion stability of the phosphorus-based heat stabilizer Thus, any slurry can be used as long as it can maintain a slurry property with high fluidity and does not hinder the production reaction of the terminal-modified propylene polymer.

  Among the aforementioned solvents, toluene, xylene, and o-dichlorobenzene are highly compatible with the terminal-modified propylene polymer grown in the heating reaction system. For example, the reaction system before the addition of the solvent and the solvent Is preferable because it does not disturb the reaction system such as phase separation and heterogeneity, and o-dichlorobenzene is particularly preferable because of its high compatibility at high temperatures.

  A solvent may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The phosphorus-based heat stabilizer is preferably an organic phosphorus compound selected from the group of organic phosphate metal salts, phosphites and phosphonites, and mixtures thereof. Among these, phosphites and phosphonites are particularly effective because of the high thermal stabilization effect of the terminal-modified propylene polymer at the time of production and excellent durability such as hydrolysis resistance of the terminal-modified propylene polymer after production. More preferred is phosphite, particularly preferred.

  The organic phosphate metal salt is preferably a compound represented by the following formula (20) or (21).

(Wherein R ₅ and R ₆ are each independently an alkyl group having 1 to 30 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, octadecyl, cyclohexyl, stearyl, etc.) Or an aryl group having 6 to 30 carbon atoms such as phenyl, nonylphenyl, butylphenyl, butylmethylphenyl, dibutylphenyl, dibutylmethylphenyl, biphenyl, octylphenyl, etc. M is a periodic table, excluding hydrogen and carbon It is a group 1 to group 15 metal element, specifically composed of, for example, titanium, zirconium, tin, antimony, cerium, germanium, zinc, cobalt, manganese, iron, aluminum, magnesium, calcium, strontium, sodium and potassium. At least one selected from the group Represents more metals, x is represents the valence of the metal.)

R ₅ and R ₆ are not particularly limited, but usually have a carbon number of 6 to 6 such as hexyl, octyl, decyl, dodecyl, octadecyl, cyclohexyl, stearyl and the like because of excellent compatibility with the terminal-modified propylene polymer. 30 alkyl groups are preferable, and M is preferably zinc, magnesium, calcium, or aluminum because of low toxicity, and among them, zinc is particularly preferable.

  Specific examples of the organic phosphate metal salt include magnesium stearyl phosphate (LBT-1812), aluminum stearyl phosphate (LBT-1813), calcium stearyl phosphate (LBT-1820), and zinc manufactured by Sakai Chemical Industry Co., Ltd. Examples include stearyl phosphate (LBT-1830). Among these, calcium stearyl phosphate (LBT-1820) and zinc stearyl phosphate (LBT-1830) are preferable because the heat-stabilizing ability of the terminal-modified propylene polymer is high.

  The phosphite is preferably a compound represented by the following formula (22).

(In the formula, R ₇ , R ₈ and R ₉ are each independently, for example, 1 to 30 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, octadecyl, cyclohexyl, stearyl, etc. Or an aryl group having 6 to 30 carbon atoms such as phenyl, nonylphenyl, butylphenyl, butylmethylphenyl, dibutylphenyl, dibutylmethylphenyl, biphenyl, octylphenyl, etc.)

  Specifically, examples of these compounds are tris- (2,4-di-t-butylphenyl) phosphite, tetrakis- (2,4-di-t-butylphenyl) -4,4′-biphenylene. Phosphite, bis- (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis- (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl- Pentaerythritol-diphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4-butylidenebis (3-methyl-6-t-butylphenyl-di-tridecyl) phos Phyto, 1,1,3-tris- (2-methyl-4-tridecyl phosphite-5-tert-butylphenyl) butane, tris- (noni Phenyl) phosphite and 4,4'-isopropylidene-bis - (phenyl - dialkyl phosphite), and the like. Among these, tris- (2,4-di-t-butylphenyl) phosphite, tetrakis- (2,4-, which gives high thermal stability to the terminal-modified propylene polymer molecules grown in the reaction vessel. Di-t-butylphenyl) -4,4'-biphenylene phosphite, bis- (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis- (2,6-di-t-butyl- 4-methylphenyl) pentaerythritol diphosphite, among others, tris- (2,4-di-t-butylphenyl) phosphite, bis- (2,6-di-t-butyl-4-methyl) Phenyl) pentaerythritol diphosphite is preferred.

  The phosphonite is preferably a compound represented by the following formula (23).

(Wherein R ₁₀ , R ₁₁ and R ₁₂ are each independently, for example, 1-30 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, octadecyl, cyclohexyl, stearyl, etc. Or an aryl group having 6 to 30 carbon atoms such as phenyl, nonylphenyl, butylphenyl, butylmethylphenyl, dibutylphenyl, dibutylmethylphenyl, biphenyl, octylphenyl, etc.)

Specific examples of the phosphonite include tetrakis- (2,4-di-t-butylphenyl) -1,1-biphenyl-4,4′-diylbisphosphonite and tetrakis- (2,4-diphenyl). -T-butyl-5-methylphenyl) -1,1-biphenyl-4,4'-diylbisphosphonite and the like, preferably tetrakis- (2,4-di-t-butyl-5-methyl) Phenyl) -1,1-biphenyl-4,4′-diylbisphosphonite.
Its structural formula is shown in the following formula (24).

  Among the phosphorus-based heat stabilizers described above, Tris- () has been proven to give high thermal stability to the terminal-modified propylene polymer molecules grown in the reaction tank, and is inexpensive and has a proven record of safety. 2,4-di-t-butylphenyl) phosphite (for example, Irgafos 168 manufactured by Ciba Japan Co., Ltd.) is particularly preferable.

  The total amount of the phosphorus-based heat stabilizer introduced is usually 0.00010% by weight or more and 0.0010% by weight with respect to the weight of the terminal vinyl-modified propylene-based polymer that is the material to be modified introduced into the reaction vessel. % Or more, preferably 0.010% by weight or more, more preferably 0.10% by weight or more, still more preferably 0.30% by weight or more, and particularly preferably 0.40% by weight or more. The upper limit is usually 30.0% by weight or less, more preferably 20.0% by weight or less, further preferably 15.0% by weight or less, and particularly preferably 12.0% by weight or less. By introducing the amount of the phosphorus-based heat stabilizer above the lower limit, the effect of the phosphorus-based heat stabilizer can be effectively obtained. The bleeding out of the agent can be prevented. In addition, when using together 2 or more types of phosphorus thermal stabilizers, it is preferable that the total of those usage-amounts satisfy | fill the said range.

[2-2-6. Radical generator]
Unless the effect of the composition of the present invention is significantly impaired, the radical-generating agent alone or the radical generator is added to the reaction system for producing the terminal-modified propylene polymer [2-2-3. Add a solution diluted with the solvent listed in the section of “Solvent”, a chain transfer agent, and a polymerization inhibitor to promote the reaction, or to obtain a molecular weight and molecular weight distribution of the resulting terminal-modified propylene polymer, and further a branched structure. It is also possible to adjust.

  Any radical generator can be used as the radical generator used in the production of the terminal-modified propylene polymer of the present invention as long as the effects of the present invention are not significantly impaired. Specific examples thereof include t-butyl peroxyisopropyl monocarbonate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxy (2-ethylhexyl) monocarbonate, t-butyl peroxyallyl monocarbonate, diisopropyl peroxydicarbonate, di- Examples thereof include n-propyl peroxydicarbonate, di-s-butyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, 1,6-bis (t-butylperoxycarbonyloxy) hexane and the like. Specific product names include, for example, Perbutyl I (Nippon Yushi Co., Ltd.), Perhexyl I (Nippon Yushi Co., Ltd.), Perbutyl E (Nippon Yushi Co., Ltd.), Peromer AC (Nippon Yushi Co., Ltd.), Parroyl SBP (Nippon Yushi Co., Ltd.). Etc.

  Among these, t-butyl peroxyisopropyl monocarbonate and t-hexyl peroxyisopropyl monocarbonate are preferable, and t-butyl peroxyisopropyl monocarbonate is more preferable. A radical generator may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

The production method using a solvent such as the suspension method and the solution method provides mild reaction conditions for the production of the terminal-modified propylene polymer as described above as an example of the solution method. As a result, the production reaction rate of the terminal-modified propylene polymer is high, the terminal olefin part of the terminal vinyl-modified propylene polymer is highly selectively modified to the modifying group (1), and the raw material molecular chain or grows. It is excellent in that generation of internal olefin sites, branch sites and gelling sites in the molecular chain can be effectively suppressed. Furthermore, suppressing the generation of internal olefin sites, branch sites and gelation sites can further enhance the effect by adding an antioxidant. In addition, the production reactivity of the terminal-modified propylene polymer is sufficient.
On the other hand, the radical generator promotes the generation of internal olefin sites, branch sites and gelation sites. Therefore, it is preferable not to add a radical generator in the present invention. However, when a radical generator is used for the purpose of increasing the reactivity, for example, in order to prioritize productivity, it is better to keep the amount used as follows for the above reasons.

  In the suspension method and the solution method, the quality of the terminal-modified propylene polymer deteriorates, but priority is given to productivity. Therefore, when a radical generator is used, the amount used is the amount of the terminal-modified propylene polymer obtained. The radical generator is usually 0.00010 parts by weight or more, preferably 0.0005 parts by weight or more, more preferably 0.001 parts by weight or more, still more preferably 0.005 parts by weight or more, based on 100 parts by weight. From the viewpoint, 0.01 part by weight or more is more preferable, and the upper limit thereof is usually 1.0 part by weight or less and 0.50 part by weight of the radical generator with respect to 100 parts by weight of the obtained terminal-modified propylene polymer. The following is more preferable, and 0.10 parts by weight or less is particularly preferable.

  On the other hand, when a terminal-modified propylene polymer is produced by a melting method, since the concentration of the raw material in the reaction system is high because no solvent is used, the terminal vinyl-modified propylene polymer is compared with the suspension method and the solution method. It is preferable not to add a radical generator because the reaction rate between the terminal olefin part and the modifying agent is high and the modification reaction can be performed for a necessary time as compared with the melt-kneading method. Even when a radical generator is used in order to prioritize productivity, for the above reasons, the amount used should be kept to a very small amount as described below.

  In the melting method, the quality of the terminal-modified propylene polymer is deteriorated, but priority is given to productivity. Therefore, when a radical generator is used, the amount used is 100 parts by weight of the terminal-modified propylene polymer obtained. On the other hand, the radical generator is usually 0.00010 part by weight or more, more preferably 0.0005 part by weight or more, more preferably 0.001 part by weight or more, further preferably 0.005 part by weight or more, from the viewpoint of promoting the reaction. The upper limit is more preferably 0.01 parts by weight or more, and the upper limit is usually 1.0 parts by weight or less for radical generators and 100 parts by weight or less for 100 parts by weight of the resulting terminal-modified propylene polymer. The amount is preferably 0.10 parts by weight or less.

  In the case of producing a terminal-modified propylene polymer by a melt kneading method, since the reaction time is as short as several minutes, a method of accelerating the reaction with a radical generator is preferably used. In this case, the amount of use is usually 0.0010 parts by weight or more, more preferably 0.0050 parts by weight or more, more preferably 0.010 parts by weight, based on 100 parts by weight of the terminal-modified propylene-based polymer obtained. The above is more preferable, 0.050 part by weight or more is further preferable, and from the viewpoint of promoting the reaction, 0.10 part by weight or more is more preferable, and the upper limit thereof is 100 parts by weight of the terminal-modified propylene polymer to be obtained. The radical generator is usually 10 parts by weight or less, more preferably 5.0 parts by weight or less, still more preferably 3.0 parts by weight or less, and particularly preferably 1.0 parts by weight or less.

[2-3. Reaction / separation / purification / drying equipment and conditions]
[2-3-1. Reaction / separation / purification equipment and conditions in the melting, suspension, or solution method
[2-3-1-1. apparatus]
The reaction apparatus for producing the terminal-modified propylene polymer of the present invention by a melting method, suspension method or solution method is optional as long as the composition of the present invention is obtained by containing the produced terminal-modified propylene polymer. However, it can usually be produced using a known reaction apparatus.

Specifically, the reaction apparatus for producing the terminal-modified propylene-based polymer batch-wise is not particularly limited. For example, a known vertical or horizontal stirred tank reactor can be used.
The reaction apparatus for continuously producing the terminal-modified propylene polymer is not particularly limited. For example, a known vertical stirring complete mixing tank, vertical thermal convection mixing tank, tower-type continuous reaction tank A horizontal stirring polymerization tank or the like can be used.
In addition, each of these reaction apparatuses may be used alone or in any combination of two or more.

In these facilities, when using a modifier that is easily sublimated or vaporized, a tank capable of collecting the sublimated or vaporized components should be provided in the reaction tank and in the vicinity of the reaction tank in the line connected to the atmosphere. However, it is preferable for reasons such as production stability and safety.
In addition, when a solvent is used, it is preferable to install a reflux facility in the vicinity of the reaction tank in order to prevent the solvent from being distilled off from the reaction tank.
Moreover, in order to extract reusable components, such as unreacted modifiers and solvents, it is industrially preferable to install these recycling facilities.

  Any known separation / purification method for the terminal-modified propylene polymer obtained by the reaction, for example, reprecipitation method, extraction method represented by liquid-liquid extraction or solid-liquid extraction, separation method by molecular size, ion An apparatus for separation / purification by a separation / purification method such as a separation method using an exchange resin or a filter separation method is optional as long as the composition of the present invention can be obtained by containing a terminal-modified propylene polymer. It can be produced using a known separation / purification apparatus.

  Specifically, also in the separation / purification method described above, a batch separation / purification method and / or a continuous separation / purification method are usually used, and a separation / purification device corresponding to these can be used. it can. In addition, each of these separation / purification devices may be used alone or in any combination of two or more.

In the case of using a solvent in the separation / purification, it is preferable to install a reflux facility in the vicinity of the reaction tank in order to prevent the solvent from being distilled off from the reaction tank.
Moreover, in order to extract reusable components, such as unreacted modifiers and solvents, it is industrially preferable to install these recycling facilities.

The equipment for drying the terminal-modified propylene polymer of the present invention is optional as long as the composition of the present invention can be obtained by containing the produced terminal-modified propylene polymer of the present invention. It can be manufactured using an apparatus.
Specific examples include a drying tank directly connected to a vacuum pump and a blast drying tank in which a dry gas (air or inert gas) circulates, and the terminal-modified propylene polymer is dried in these drying tanks. Is possible. Moreover, when passing through intermediate tanks, such as a silo, before packing a terminal modified propylene polymer, it is also used suitably to distribute | circulate said dry gas in the said intermediate | middle layer and to dry. Here, the inert gas is an inert gas such as nitrogen or argon.

[2-3-1-2. conditions]
Conditions such as reaction temperature, reaction atmosphere, reaction pressure, and reaction time in the production of the terminal-modified propylene polymer are arbitrary as long as the effects of the present invention are not significantly impaired.

  However, the reaction temperature between the terminal olefin portion of the terminal-modified propylene polymer and the modifier is usually 130 ° C. or higher, preferably 150 ° C. or higher, more preferably 160 ° C. or higher, further preferably 165 ° C. or higher. 170 degreeC or more is especially preferable from a viewpoint of productivity. Further, the upper limit of the reaction temperature is usually 300 ° C. or less, preferably 250 ° C. or less, more preferably 230 ° C. or less, further preferably 210 ° C. or less, and the heat of the growing molecules in the reaction system tank by the heat-induced side reaction. In order to suppress undesired deterioration in physical properties and quality such as molecular weight reduction due to decomposition and generation of unnecessary double bonds in the molecule, 200 ° C. or lower is particularly preferable.

The reaction atmosphere is usually preferably an inert gas atmosphere such as nitrogen or argon. These gases may be used alone or in combinations of two or more in any ratio and combination. Industrially, an inexpensive nitrogen atmosphere is preferable.

  Furthermore, the reaction pressure is usually 95.0 kPa or more and 101.3 KPa or more and 103.0 KPa or more. The upper limit of the reaction pressure is usually 1013 KPa or less, preferably 500 KPa or less, more preferably 300 KPa or less, further preferably 200 KPa or less, and particularly preferably 150 KPa or less for reasons such as production safety.

  The reaction time is usually 1 hour or longer, and the upper limit is usually 200 hours or shorter, more preferably 150 hours or shorter, more preferably 120 hours or shorter, and 110 hours or shorter is a reaction system tank by a heat-induced side reaction. In particular, it is particularly preferable because it is possible to suppress undesirable physical properties and quality degradation, such as a decrease in molecular weight due to thermal decomposition of the growing molecules and generation of unnecessary double bonds in the molecules.

  The ratio of the number of molecules of the modifier to the number of molecules of the terminal vinyl-modified propylene polymer that is the raw material to be modified supplied to the reaction tank is usually 2000 equivalents or less, preferably 1500 equivalents or less, and more preferably 1200 equivalents or less, 1000 equivalents or less is particularly preferable from the viewpoint of cost related to the modifier. Further, the lower limit is usually 1 equivalent or more, preferably 10 equivalents or more, more preferably 50 equivalents or more, still more preferably 100 equivalents or more, still more preferably 500 equivalents or more, and particularly preferably 800 equivalents or more from the viewpoint of reactivity. preferable.

  Conditions such as temperature, atmosphere, pressure and time in the separation and purification of the produced terminal-modified propylene polymer are arbitrary as long as the effects of the present invention are not significantly impaired.

  For example, in the case of the reprecipitation method, the temperature is usually equal to or lower than the boiling point of the poor solvent used for reprecipitation at normal pressure, particularly when a poor solvent having a boiling point exceeding 50 ° C. is used. The temperature is preferably 50 ° C. or lower from the viewpoint of reducing the facility capacity during adjustment. In addition, the lower limit is above the freezing point, but it is usually preferable that the lower limit is higher than the room temperature in the cold season such as winter from the viewpoint of reducing the facility capacity by adjusting the temperature in the same manner as described above.

  As the poor solvent, a solvent having a boiling point exceeding the temperature in the high temperature period at the place of use and having a freezing point lower than the temperature in the cold period is preferable from the viewpoint of the facility capacity. For example, ketones such as acetone, alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol can be preferably used. Among these, inexpensive acetone that does not contain active hydrogen can be preferably used.

  The atmosphere in separation / purification is usually preferably an inert gas atmosphere such as nitrogen or argon. These gases may be used alone or in combinations of two or more in any ratio and combination. Industrially, an inexpensive nitrogen atmosphere is preferable.

  Usually, the separation / purification pressure is preferably normal pressure.

  Further, the reprecipitation time is arbitrary as long as the composition of the present invention can be obtained by containing a purified terminal-modified propylene polymer, but is appropriately appropriate depending on the scale of the tank to be used, the kind of the poor solvent, and the like. Time is enough.

  The number of reprecipitations is arbitrary as long as the composition of the present invention can be obtained by containing a purified terminal-modified propylene polymer, but is usually more preferably once or more and twice or more. The upper limit is preferably 3 times or less because it is industrially advantageous.

  Regarding the drying temperature and drying time, it is preferable that the drying is performed under the condition that the temperature is less than the melting point of the terminal-modified propylene polymer and does not block, and the terminal-modified propylene polymer is not thermally deteriorated. The drying temperature is appropriately selected according to the conditions such as the drying equipment and equipment scale used, the terminal-modified propylene polymer filling amount, and the residual volatile component amount. In the atmosphere in the tank, air may be used if there is no fear of flammability or explosiveness, but in such a case, an inert gas, particularly inexpensive nitrogen, is preferably used. it can.

[2-3-2. Reaction, apparatus and conditions in melt kneading method]
The reaction apparatus for producing the terminal-modified propylene polymer of the present invention by the melt-kneading method is optional as long as the composition of the present invention can be obtained by containing the produced terminal-modified propylene polymer, but generally known It can be produced using a reactor.

Specifically, usually, batch type kneaders such as rolls, internal mixers, Banbury mixers, kneaders, Brabenders, etc., one-stage type, two-stage continuous type kneaders, twin screw extruders, single It can be melt-kneaded by an axial screw extruder or the like. Also, tumbler blender, ribbon blender, V
It is also suitable to use a kneading apparatus for melt kneading after uniform mixing with a mold blender, Henschel mixer or the like. Among these, a twin screw extruder and a single screw extruder are preferable. Examples of the kneading method include a method of mixing various additives in a place where the mixture is melted by heating. In addition, blending oils and the like can be used for the purpose of uniformly dispersing various additives. One type of kneading apparatus may be used alone, or two or more types may be used in any combination. Moreover, the kneading | mixing method may be performed individually by 1 type, and may be performed combining 2 or more types arbitrarily.

  In these facilities, when using a modifier that is easily sublimated or vaporized, a tank capable of collecting the volatile component is provided between the outlet of the volatile component from the kneading tank and the atmosphere, or It is preferable to install a disposal facility with sufficient capacity for reasons such as manufacturing stability and safety, and hygiene management.

  The kneading temperature is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 150 ° C. or higher, preferably 160 ° C. or higher, more preferably 170 ° C. or higher, more preferably 180 ° C. or higher, and the upper limit is The temperature is usually 300 ° C. or lower, preferably 250 ° C. or lower, more preferably 240 ° C. or lower, and further preferably 230 ° C. or lower. When the kneading temperature is equal to or higher than the lower limit, the kneaded material can be sufficiently melted and easily and sufficiently kneaded. On the other hand, when the kneading temperature is equal to or lower than the upper limit, the kneaded material or the like is thermally decomposed. Thus, the molecular weight is reduced, and the cross-linking reaction involving the radicals generated by heat induction proceeds to prevent the gel component from being generated.

  The kneading time cannot be generally determined depending on the type of kneading apparatus, the propylene-based polymer species to be kneaded, and the type of radical generating species when adding a very small amount of radical generating species, but it is generally 0. 1 minute or more and usually 20 minutes or less. In the case of kneading with a roll, it is more preferable to carry out in 5 minutes or less. In the case of kneading with a Banbury mixer, a kneader, or a Brabender, it is usually preferably 3 minutes or more and 10 minutes or less, particularly preferably 5 minutes or less. In the case of kneading with an extruder, it is preferably within 3 minutes, more preferably within 2 minutes, within 1 minute from the viewpoint of suppressing thermal deterioration of the kneaded propylene polymer and the productivity of kneading production of the composition. Is particularly preferred.

  The number of kneading and stirring is arbitrary as long as the produced resin composition has the characteristics to be provided as the composition of the present invention. It ’s fine. As an example, when kneading on a scale of 100 g to 50 g is performed with a Brabender kneader, it is usually preferably 50 rpm or more and preferably 100 rpm or more, and the upper limit is 200 rpm or less, and further 150 rpm or less can be sufficiently kneaded, and propylene The rotation speed is preferably used because deterioration such as molecular cutting of the polymer can be suppressed.

[3. Modified propylene polymer composition]
[3-1. Usage]
In general, polyolefin resins such as polypropylene are excellent in moldability, heat resistance, water vapor barrier properties, chemical resistance, heat sealing properties, solvent resistance, mechanical properties, appearance, etc. It is necessary to improve the properties such as physical properties (flavor properties, aromaticity) and design properties (surface glossiness, transparency) in addition to the above properties by adopting a multilayer structure with other types of resins. is there.

  The modified propylene polymer composition of the present invention is placed between layers to be bonded in order to form a multilayer structure for the purpose of improving the above-mentioned characteristics of such polyolefin resin, and has excellent adhesive properties. Show.

The modified propylene polymer composition of the present invention comprising the terminal modified propylene polymer of the present invention as a main component can be suitably used for adhesion of a layer comprising the following resin or resin composition.
Here, the modified propylene polymer composition containing the terminal modified propylene polymer of the present invention as a main component is 50% by weight or more, preferably 60% by weight or more of the terminal modified propylene polymer of the present invention. More preferably, it is 70% by weight or more and usually contains 100% by weight or less, and is usually obtained by carrying out the reaction, separation, purification and drying by the above-mentioned method for producing the terminal-modified propylene polymer of the present invention. Various additives such as an antioxidant other than the diluted resin in the production of the composite resin composition of the present invention to be described later are added to the terminal-modified propylene polymer obtained or the terminal-modified propylene polymer as necessary. This refers to the one prepared.

  Specific examples of a resin and a resin composition as a base material for forming an adherend layer to be bonded by the modified propylene polymer composition of the present invention include polyolefin resins such as polypropylene resins and polyethylene resins; Styrene resins such as polystyrene, polystyrene for impact resistance, and styrene / methacrylic acid copolymers (hereinafter collectively referred to as “PS resins”); polyethylene terephthalate (PET), polybutylene terephthalate (PBT), PES resins such as polyethylene naphthalate (PEN), polycyclohexylene terephthalate (PCT), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), and polylactic acid (PLA) ; Polycarbonate Resin (hereinafter collectively referred to as “PC resin”); acrylic resin such as polyacrylonitrile, acrylonitrile / methyl acrylate / butadiene copolymer, polymethyl methacrylate (hereinafter collectively referred to as “PC resin”). EVOH having an ethylene content of 15 to 65 mol% and a saponification degree of 90% or more; a resin such as a PA resin such as nylon 6 or nylon 66, or these resins A resin composition is mentioned. The adherend layer to be bonded may be composed of the above-mentioned resin or a single resin composition containing the above-mentioned resin, or may be composed of two or more arbitrary combinations and ratios.

  Among these, in particular, the modified propylene polymer composition of the present invention is an adherend layer having the polarity of the modifying group (1) and the reactive substituents and bonds of the terminal modified propylene polymer of the present invention. And particularly excellent in adhesion between the propylene unit (3) of the terminal-modified propylene polymer and the adherend layer exhibiting strong hydrophobic interaction. Examples of the adherend layer having the polarity of the modifying group (1) of the terminal-modified propylene-based polymer and the reactive substituent or bond include an adherend layer containing PES resin, EVOH, and the like. Examples of the adherend layer exhibiting a strong hydrophobic interaction with the propylene unit (3) of the modified propylene polymer include an adherend layer containing a polyolefin resin such as a polypropylene resin and a polyethylene resin.

  The modified propylene polymer composition of the present invention can also be widely used when laminating the same or different materials selected from metals such as steel plates and aluminum foils.

[3-2. Diluted resin]
In order for the composition of the present invention to exhibit sufficient adhesiveness, the amount of the modifying group (1) contained in the composition is important.
For the same reason, in order for the composition of the present invention to exhibit sufficient adhesiveness, the amount of the terminal-modified propylene polymer of the present invention having the modifying group (1) contained in the composition at the molecular end is important. become.

  Although the modified propylene polymer composition of the present invention can be used alone as an adhesive resin, the amount of the modifying group (1) and the amount of the terminal modified propylene polymer contained in the composition as described above. In order to adjust this, dilution with other resins can also be suitably used. Hereinafter, the resins to be diluted are collectively referred to as “diluted resin” as appropriate.

  As the dilution resin, any of the dilution resins shown below may be used as long as the composite resin composition obtained by diluting the terminal-modified propylene polymer exhibits various properties intended in the present invention. it can.

Specific examples of the dilution resin include polyolefin resins such as polypropylene resins and polyethylene resins already described above, PS resins, PES resins, PC resins, PAN resins, PA resins, and the like. Can be appropriately selected and used according to the purpose. Dilution resin may be used individually by 1 type, and what consists of arbitrary combinations and ratios in 2 or more types may be used. However, since the modifying group (1) contained in the composition of the present invention easily reacts with, for example, a hydroxyl group or the like, it is a resin having a substituent or bond that is reactive with the modifying group (1) including a hydroxyl group. When diluting, care must be taken not to raise the temperature more than necessary. Therefore, among these, it is particularly preferable to use a polyolefin resin such as polyethylene or polypropylene that is not reactive with the modifying group (1) as a dilution resin.
The composite resin composition of the present invention is obtained by diluting the modified propylene-based polymer composition of the present invention with such a diluted resin.

[3-3. Content of Modified Group (1) in Composition]
The content of the modified group (1) contained in the modified propylene-based polymer composition or composite resin composition of the present invention is usually 0.8 because the adhesive strength between the adherend layers for forming a laminated structure is sufficiently obtained. 015% by weight or more, preferably 0.018% by weight or more, more preferably 0.020% by weight or more from the viewpoint of adhesion, and the upper limit is usually 0.20% by weight or less, and 0.18% by weight or less. Preferably, 0.16% by weight or less is more preferable, 0.14% by weight or less is more preferable, 0.12% by weight or less is even more preferable, and sufficient adhesive properties are obtained even with a small amount of the modifying group (1) content. In order to effectively exhibit the advantage of the composition of the present invention that is advantageous in terms of cost, 0.10% by weight or less is particularly preferable.

  In addition, the content of the terminal-modified propylene polymer contained in the modified propylene polymer composition or composite resin composition of the present invention is sufficient to obtain an adhesive force between the layers for forming the laminated structure. Usually 3.0% by weight or more, preferably 4.0% by weight or more, more preferably 5.0% by weight or more, further preferably 6.0% by weight or more, and 7.0% by weight or more from the viewpoint of adhesiveness. Particularly preferred. The upper limit is usually 100% by weight or less, preferably 60% by weight or less, more preferably 40% by weight or less, still more preferably 35% by weight or less, still more preferably 30% by weight or less, and a small amount of modifying groups ( Even when the content of 1) is sufficient, sufficient adhesive properties can be obtained, and in order to effectively exhibit the advantage of the composition of the present invention that it is advantageous in terms of cost, 25% by weight or less is particularly preferable.

[3-4. Content of unreacted modifier]
The modified propylene polymer composition or composite resin composition of the present invention may contain an unreacted modifier remaining in the production process of the terminal-modified propylene polymer of the present invention.

  The content of the unreacted modifier in the modified propylene polymer composition or composite resin composition of the present invention is usually 0% by weight or more, preferably 0.0000010% by weight or more, and 0.0000050% by weight or more. More preferably, 0.000010% by weight or more is further preferable, 0.000050% by weight or more is further preferable, 0.00010% by weight or more is further more preferable, 0.00050% by weight or more is particularly preferable. Usually 0.30% by weight or less, preferably 0.20% by weight or less, more preferably 0.10% by weight or less, further preferably 0.010% by weight or less, further preferably 0.0080% by weight or less, 0050% by weight or less is particularly preferable. When the content of the unreacted modifier is equal to or more than the above lower limit, it is possible to suppress an increase in a load such as a purification equipment requirement in the purification process and to suppress a manufacturing cost. Further, when the content of the unreacted modifier is not more than the above upper limit, bleed out of the unreacted modifier or unreacted modifier is not preferable. Problems such as the reaction of the unreacted modifying agent with the site where the modifying group (1) in the coalescence is preferably reacted are prevented.

  The content of the unreacted modifier in the composition of the present invention can be determined by FT-IR.

[3-5. Method for producing modified propylene polymer composition or composite resin composition]
The composite resin composition of the present invention is prepared by mixing the above-described diluted resin, antioxidant and other additives in the modified propylene polymer composition of the present invention as a kneading device, for example, a roll, an internal mixer, Manufactured by melt-kneading with batch-type kneaders such as Banbury mixers, kneaders, Brabenders, etc., one-stage type, two-stage type continuous kneaders, twin-screw extruders, single-screw extruders, etc. be able to. In addition, these are previously tumbler blender, ribbon blender, V
It is also suitable to use a kneading apparatus for melt kneading after uniform mixing with a mold blender, Henschel mixer or the like. Among these, the use of a twin screw extruder or a single screw extruder is preferable. Examples of the kneading method include a method of mixing various additives in a place where the resin component is heated and melted. In addition, blending oils and the like can be used for the purpose of uniformly dispersing various additives. One type of kneading apparatus may be used alone, or two or more types may be used in any combination. Moreover, the kneading | mixing method may be performed individually by 1 type, and may be performed combining 2 or more types arbitrarily.

  The kneading temperature is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 150 ° C. or higher, preferably 160 ° C. or higher, more preferably 170 ° C. or higher, more preferably 180 ° C. or higher, and the upper limit is The temperature is usually 300 ° C. or lower, preferably 250 ° C. or lower, more preferably 240 ° C. or lower, and further preferably 230 ° C. or lower. When the kneading temperature is equal to or higher than the lower limit, the resin component to be kneaded can be sufficiently melted and easily and sufficiently kneaded. On the other hand, when the kneading temperature is not more than the above upper limit, the resin component to be kneaded is thermally decomposed to lower the molecular weight, or a crosslinking reaction involving a radical generated by heat induction proceeds to generate a gel component. Is prevented.

  The kneading time cannot be generally specified depending on the type of kneading apparatus, the type of resin to be kneaded, and the type of radical generating species when adding a very small amount of radical generating species, but usually 0.1 minutes or more. Usually, it is 20 minutes or less. In the case of kneading with a roll, it is more preferable to carry out in 5 minutes or less. In the case of kneading with a Banbury mixer, a kneader, or a Brabender, it is usually more preferably 3 minutes to 10 minutes and more preferably 3 minutes to 5 minutes. In the case of kneading with an extruder, it is preferably within 3 minutes, more preferably within 2 minutes, and particularly preferably within 1 minute from the viewpoint of suppressing thermal deterioration of the kneaded resin and productivity of kneading production of the composition.

  The number of kneading and stirring is arbitrary as long as the produced resin composition has the characteristics that should be provided as the composite resin composition of the present invention. What should I do? As an example, when kneading on a scale of 100 g to 50 g is performed with a Brabender kneader, it is usually preferably 50 rpm or more and 100 rpm or more, and the upper limit is 200 rpm or less, and further 150 rpm or less can be sufficiently kneaded. Since the deterioration such as molecular cutting of the resin component can be suppressed, the rotation speed is suitably used.

[3-6. Antioxidant]
When kneading and preparing the modified propylene polymer composition or composite resin composition of the present invention, it is preferable that an antioxidant be present in the kneading system.

That is, at the time of manufacture and molding of the composition, the composition is held under heating conditions. At this time, for example, it is common that radicals are generated by the extraction of hydrogen atoms in the molecular chain of a resin component, particularly a propylene-based polymer, due to heat induction, and this contributes to the generation of olefins in the molecular chain. Well known.
It is extremely important that the amount of these olefins not be unnecessarily increased as in the production reaction of the terminal-modified propylene polymer. For example, a branching reaction caused by the generated radicals occurs during the above heating, which causes fish eyes due to gelation in the obtained resin, composition, molded article, and problems such as poor appearance. cause. Further, due to the branching, the melt is gelled in a manufacturing machine, a kneading machine, and a molding machine to cause manufacturing, kneading or molding troubles. In addition, various problems such as inability to obtain stability during kneading due to thickening are caused.

  For this reason, at the time of manufacture of the composition of the present invention or at the time of molding using the same, the branching reaction caused by the above-mentioned radicals generated by heat induction is suppressed, and the occurrence of fish eyes and the like which are the basis of the appearance defect is suppressed. Therefore, for example, an antioxidant is added in order to facilitate manufacturing or molding management so that the gelled product that has stayed in the manufacturing machine or molding machine becomes huge and does not cause trouble in manufacturing or molding. It is preferable.

  That is, as a result of intensive studies to solve the above problems, the present inventors have introduced a specific amount of a specific antioxidant at the time of producing the composition of the present invention or molding using the composition. Thus, it has been found that it is possible to provide a method for greatly suppressing various problems caused by the gelation.

  The method of introducing the antioxidant when producing the composition of the present invention is not particularly limited as long as the effect of the above antioxidant is exhibited. As an introduction method, specifically, the antioxidant may be introduced after blending with the raw material particles of the composition or while blending, or it may be introduced into the raw material resin-containing melt and kneaded. It is. When introduced into a resin-containing melt as a raw material, the antioxidant may be introduced alone if it is a solid antioxidant, or the liquid is used if it is a liquid raw material as a solvent or composition raw material. It may be introduced as a slurry. The solvent thus introduced is removed from a decompressed vent or the like. In addition, as a solvent [2-2-3. Those mentioned in the section of [Solvent] can be used. In the case of introducing the antioxidant as a slurry, the property of the slurry is preferably a property in which the antioxidant particles are stably dispersed in the slurry and hardly settled. Therefore, in addition to stirring as described above, it is preferable to increase the slurry viscosity by setting the antioxidant concentration of the slurry to a high concentration of 5% by weight or more.

  The antioxidant used in the composition of the present invention is [2-2-4. The various antioxidants exemplified in the section of “Antioxidants” alone or a mixture thereof are used. Among them, dibutylhydroxytoluene (BHT; 2,6-dibutyl-4-methylphenol), pentaerythritol tetrakis [3- (3,5-di-tert) are easily available, inexpensive and highly effective. -Butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxy) benzene, Dibutylhydroxytoluene (BHT; 2,6-dibutyl-4-methylphenol) and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] are more preferable because they are less colored. .

  Further, the content of the antioxidant is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.0010% by weight or more, preferably 0.010% by weight or more, based on the composition of the present invention. More preferably 0.020% by weight or more, more preferably 0.030% by weight or more, still more preferably 0.040% by weight or more, particularly preferably 0.050% by weight or more, and the upper limit is usually 0.50. % By weight or less, preferably 0.30% by weight or less, more preferably 0.20% by weight or less, more preferably 0.15% by weight or less, still more preferably 0.10% by weight or less, particularly preferably 0.080% by weight. % Or less. When the content of the antioxidant is equal to or higher than the above lower limit, the effect of addition can be effectively exhibited. The bleeding out of the agent can be prevented. In addition, when using together 2 or more types of antioxidant, it is preferable that the total of those usage-amounts satisfy | fill the said range.

[3-7. Phosphorus heat stabilizer]
When kneading and preparing the modified propylene polymer composition or composite resin composition of the present invention, it is preferable that a phosphorous heat stabilizer coexist in the kneading system.

  That is, at the time of manufacturing and molding the composition, the composition is held under heating conditions. At this time, there is a problem that the resin component in the composition is reduced in molecular weight by heat and molecular chain scission, but by adding and kneading a phosphorus-based heat stabilizer to the kneading system, such low molecular weight can be achieved. It can be effectively suppressed.

  The method for introducing the phosphorous heat stabilizer is not particularly limited as long as the effect of the phosphorous heat stabilizer is exhibited. As the introduction method, specifically, the phosphorous heat stabilizer may be introduced after blending with the raw material particles of the composition or while blending, or introduced into the resin-containing melt as the raw material and kneaded. Is also possible. When introduced into a resin-containing melt as a raw material, if it is a solid phosphorus heat stabilizer, it may be introduced alone, or if it is a liquid raw material as a solvent or composition raw material, You may make it introduce | transduce as a slurry using the liquid. The solvent thus introduced is removed from a decompressed vent or the like. In addition, as a solvent [2-2-3. Those mentioned in the section of [Solvent] can be used. When the phosphorus-based heat stabilizer is introduced as a slurry, it is preferable that the properties of the slurry are such that the phosphorus-based heat stabilizer particles are stably dispersed in the slurry and hardly settled. Therefore, in addition to stirring as described above, it is preferable to increase the slurry viscosity by setting the concentration of the phosphorus-based heat stabilizer in the slurry to a high concentration of 5% by weight or more.

  The phosphorus-based heat stabilizer used in the composition of the present invention is [2-2-5. The various phosphorus heat stabilizers exemplified in the section of “Phosphorus heat stabilizer” or a mixture thereof may be used. Among these, tris- (2,4-di-t-butylphenyl) phosphite and tetrakis- (2,4-di-t-butylphenyl) -4,4′-biphenylenephosphine which give high thermal stability And bis- (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis- (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, etc. Of these, tris- (2,4-di-t-butylphenyl) phosphite and bis- (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite are preferable. Tris- (2,4-di-t-butylphenyl) phosphite (for example, Irgafos 168 manufactured by Ciba Japan Co., Ltd.) is particularly preferable because it is inexpensive and has a track record in safety.

  Further, the content of the phosphorus-based heat stabilizer is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.0010% by weight or more, preferably 0.010% by weight, based on the composition of the present invention. More preferably, 0.020% by weight or more, more preferably 0.030% by weight or more, still more preferably 0.040% by weight or more, particularly preferably 0.050% by weight or more, and the upper limit is usually 0. .50% by weight or less, preferably 0.30% by weight or less, more preferably 0.20% by weight or less, more preferably 0.15% by weight or less, still more preferably 0.10% by weight or less, particularly preferably 0. 0% by weight or less. It is 080 weight% or less. When the content of the phosphorus-based heat stabilizer is equal to or higher than the above lower limit, the effect of the addition can be effectively exhibited. At the same time, bleeding out can be prevented. In addition, when using together 2 or more types of phosphorus thermal stabilizers, it is preferable that the total of those usage-amounts satisfy | fill the said range. Moreover, when a phosphorus heat stabilizer is used at the time of manufacture of a terminal modified propylene polymer, the sum total with the phosphorus heat stabilizer contained with a terminal modified propylene polymer becomes content in the said composition.

[3-8. Other various additives]
The modified propylene polymer composition or composite resin composition of the present invention can contain various additives as long as the effects of the present invention are not significantly impaired. It should be noted that the order, method, addition amount, etc., of mixing various additives into the composition of the present invention are arbitrary as long as various additives are contained in the final composition and the effects of the present invention are not significantly impaired. Can be determined.

  For example, in order to produce the composition of the present invention, the modified propylene-based polymer composition of the present invention is added to the above-mentioned antioxidants, phosphorus-based heat stabilizers, terminal-modified propylene-based polymers and After mixing the diluted resin, these various additives may be kneaded, or may be previously kneaded with the resin component of the present invention such as the above-mentioned terminal-modified propylene polymer or diluted resin. In order to produce the composition, these various additives may be kneaded together with the above main raw materials.

  Various additives can be used as long as the effects of the present invention are not significantly impaired. For example, a crystal nucleating agent, an inorganic and / or organic filler, a light resistance agent, an ultraviolet absorber, an antistatic agent, a lubricant, a fluidity improving agent, an antiblocking agent, a slipping agent, etc. Waxing agent, mold release agent, anti-fogging agent, plasticizer, colorant such as pigment or dye or carbon black, filler, compatibilizer, flame retardant, surface wettability improver, dispersion aid, various surfactants, Examples include antiseptics and fungicides. These various additives may be appropriately selected according to the purpose, and one kind may be used alone, or two or more kinds may be used in any ratio and combination.

  Specific examples of inorganic nucleating agents include talc, kaolin, montmorillonite, synthetic mica, clay, zeolite, silica, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, and barium sulfate. And metal salts such as aluminum oxide, neodymium oxide, and phenylphosphonate. In addition, these inorganic nucleating agents may be modified with an organic substance in order to enhance dispersibility in the composition of the present invention.

  On the other hand, specific examples of organic nucleating agents include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, oxalic acid Calcium, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, stearin Barium acid, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, Organic carboxylic acid metal salts such as luminium dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate; organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate; stearamide , Carboxylic acid amides such as ethylene bislauric acid amide, palmitic acid amide, hydroxy stearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide); low density polyethylene, high density polyethylene, polypropylene, polyisopropylene, polybutene, Polymers such as poly-4-methylpentene, polyvinylcycloalkane, polyvinyltrialkylsilane, and high melting point polylactic acid; ethylene-acrylic acid or methacrylic acid Sodium salt or potassium salt of a polymer having a carboxyl group such as sodium salt of copolymer, sodium salt of styrene-maleic anhydride copolymer (so-called ionomer); benzylidene sorbitol and its derivatives, sodium-2,2′-methylenebis (4 Phosphorus compound metal salts such as 6-di-t-butylphenyl) phosphate; and 2,2-methylbis (4,6-di-t-butylphenyl) sodium.

  A conventionally well-known filler can be used as a filler. Fillers are generally roughly classified into inorganic fillers and organic fillers.

Specific examples of inorganic fillers include anhydrous silica, mica, talc, titanium oxide, calcium carbonate, diatomaceous earth, allophane, bentonite, potassium titanate, zeolite, sepiolite, smectite, kaolin, kaolinite, glass, limestone, carbon , Wollastonite, Virophyllite, Sericite, Wollastonite, calcined clay, silicates such as calcium silicate, sodium silicate, precipitated calcium carbonate, heavy calcium carbonate, magnesium carbonate, aluminum oxide, calcium hydroxide, etc. , Salts of ferric carbonate, zinc oxide, iron oxide, aluminum phosphate, barium sulfate, glass fiber, basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, PMF (Proces d Mineral Fiber), xonotlite, ellestadite, Garasubarun, fly ash balloon, such as powdery, flake, fibrous fillers, or balloon-like filler and the like.
The content of the inorganic filler in the composition of the present invention is usually preferably 0% by weight or more and 1.0% by weight or more, more preferably 2.0% by weight or more, and the upper limit is usually 200% by weight or less. 150 wt% or less is preferable, and 100 wt% or less is more preferable.

Specific examples of the organic filler include raw starch, processed starch, pulp, chitin / chitosan, coconut shell powder, wood powder, bamboo powder, bark powder, kenaf, and cocoon powder.
The content of the organic filler in the composition of the present invention is preferably 0% by weight or more and usually 200% by weight or less.

  Among these, inorganic fillers are preferable, and talc is particularly preferable. In particular, talc having an average particle size of 0.1 to 40 μm is preferable.

  It should be noted that the inorganic filler is used by appropriately selecting whether its surface is untreated or surface-treated depending on the purpose. Specific examples of the surface treatment include chemical or physical treatment using a treatment agent such as a silane coupling agent, a higher fatty acid, a fatty acid metal salt, an unsaturated organic acid, an organic titanate, a resin acid, or polyethylene glycol. Can be mentioned.

  The light proofing agent has an effect of suppressing deterioration of the composition by light (that is, reduction in molecular weight). Any light-proofing agent can be used as long as the effects of the present invention are not significantly impaired. Specific examples thereof include decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (1,2 , 2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) ) Sebacate, 1- [2- [3- [3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert- Til-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5- Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] and the like Hindered amine stabilizers and the like.

  A light stabilizer may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. In particular, it is preferable to use different types of light-proofing agents in combination, and it is preferable to use them in combination with an ultraviolet absorber. Among them, it is preferable to use a combination of a hindered amine light stabilizer and an ultraviolet absorber.

  The content of the light-proofing agent in the composition of the present invention is appropriately determined according to the purpose, and is usually 0% by weight or more, preferably 0.010% by weight or more, and more preferably 0.020% by weight or more. More preferably, the upper limit is usually 10.0% by weight or less, preferably 5.0% by weight or less, more preferably 2.0% by weight or less, still more preferably 1.0% by weight or less, 0.50% or less. A weight percent or less is particularly preferred. When the content of the light proofing agent is not less than the above lower limit, the addition effect can be effectively exhibited, and by being not more than the above upper limit, the increase in the manufacturing cost due to the addition of the light proofing agent can be suppressed, and the heat resistance of the composition Problems such as inferior properties and molding processability and bleeding out of the light resistance agent can be prevented. In addition, when using 2 or more types of light resistance agents together, it is preferable that the total of those usage amount satisfy | fills the said range.

  Any ultraviolet absorber can be used as long as the effects of the present invention are not significantly impaired. Specific examples thereof include 2-hydroxy-4-n-octoxybenzophenone, 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, paraoctylphenyl salicylate, 2- (2H-benzotriazole-2 -Yl) -4-6-bis (1-methyl-1-phenylethyl) phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy ] Phenol etc. are mentioned. A ultraviolet absorber may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. In particular, it is preferable to use a combination of different types of ultraviolet absorbers, and it is also preferable to use them in combination with a light-resistant agent.

  The content of the ultraviolet absorber in the composition of the present invention is appropriately determined according to the purpose, and is usually 0% by weight or more, preferably 0.010% by weight or more, and more preferably 0.020% by weight or more. More preferably, the upper limit is usually 10.0% by weight or less, preferably 5.0% by weight or less, more preferably 2.0% by weight or less, still more preferably 1.0% by weight or less, 0.50% or less. A weight percent or less is particularly preferred. When the content of the ultraviolet absorber is not less than the above lower limit, the effect of the addition can be effectively exhibited, and when the content is not more than the above upper limit, the increase in the manufacturing cost due to the addition of the ultraviolet absorber is suppressed, and the composition It is possible to prevent problems such as poor heat resistance and molding processability and bleeding out of the UV absorber. In addition, when using 2 or more types of ultraviolet absorbers together, it is preferable that the total of those usage-amounts satisfy | fill the said range.

  As the neutralizing agent, a neutralizing agent such as hydrotalcite can be used in the composition at 0.010 wt% or more and 0.20 wt% or less.

[3-9. Method for evaluating adhesive properties]
In the present invention, in order to evaluate the adhesive properties of the composition of the present invention, an ethylene / vinyl alcohol copolymer (EVOH, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade names Soarnol DT2904 and AT4403) is used as a resin layer to be bonded. Evaluation of the adhesive properties described in 1.
When the carbon-carbon bond site formed by two carbons in the EVOH molecule is 1 unit, the amount of hydroxyl group [OH] (unit%) in EVOH used for evaluation is 71 unit% for Soanol DT2904, Soarnol AT4403 is 56 unit%.

First, by using a hot press molding machine (MiniTestPress manufactured by TOYO SEIKI) under the conditions of a temperature of 200 ° C., a pressure of 15 MPa, and a pressing time of 2 minutes (2 minutes heating → 2 minutes pressing → 2 minutes cooling) A sheet (A sheet) made of a resin composition having a length of 30 mm, a width of 30 mm, and a thickness of 0.5 mm was obtained. Each of the two types of EVOH, which are raw materials for the resin layer to be bonded, was press-molded under the same conditions to obtain an EVOH sheet (B sheet) of the above size.
Next, the A sheet is positioned on the left side, the B sheet is positioned on the right side, and both sheets are arranged side by side so that they do not overlap, and then the left A sheet is moved in the direction of the right B sheet, The A sheet overlapped with the 1 cm width on the right side from above the B sheet. A hot press molding machine was used to heat the parts where the two sheets overlap at a temperature of 200 ° C., a pressure of 15 MPa, and a press time of 2 minutes, and the two sheets were adhered (6 minutes heating → 2 minutes). Press → 2 minutes cooling).
The laminated portion of the obtained test piece was repeatedly imparted with a bend of about ± 10 mm in the vertical direction of the sheet surface, and the adhesiveness was evaluated by whether or not peeling occurred on the bonding surface. The bending in the vertical direction was performed by moving up and down twice per second, and was bent a total of 10 times.

  Since the composition of the present invention is excellent in adhesive properties, peeling does not occur on the adhesive surface in the evaluation of the adhesive properties described above.

[4. Laminate]
The laminate of the present invention includes a layer made of an adhesive resin composition made of the above-described modified propylene polymer composition or composite resin composition of the present invention, and is usually a layer made of the composition of the present invention. As a bonding layer, a laminated structure in which two layers to be bonded are interposed is adopted.

  As the form of the laminate of the present invention, a film, a sheet, a container, a tube, a bolt, etc. having a multilayer laminate structure composed of an adherend layer bonded by the composition of the present invention obtained by a coextrusion method in particular. Can be mentioned.

In addition, the thickness of the laminate of the present invention is arbitrary as long as it does not significantly impair the effects of the present invention, for example, when it is in the form of a film such as a film, sheet, laminate molded body, etc. Above, it is preferably 2 μm or more, more preferably 5 μm or more, and particularly preferably 8 μm or more. The upper limit is usually 10 mm or less, preferably 5 mm or less, more preferably 3 mm or less, and further preferably 2 mm or less.
In particular, in the case of a thin film-like molded body such as a film, the upper limit of the thickness is usually 5000 μm, preferably 3000 μm or less, more preferably 1000 μm or less, further preferably 500 μm or less, and further preferably 300 μm or less.

  It should be noted that the thickness of the adhesive layer made of the composition of the present invention contained in these laminates can be adjusted to a thickness at which sufficient adhesive strength can be obtained without excessively increasing the thickness of the entire laminate. Although it is appropriately determined according to the material of the adherend layer and the form, size and use of the laminate, it is usually 0.1 μm or more, preferably 0.5 μm or more, more preferably 1.0 μm or more, 1 The upper limit is usually 5.0 mm or less, preferably 3.0 mm or less, more preferably 2.0 μm or less, and even more preferably 1.0 μm or less.

  As a method for producing the laminate of the present invention, any method can be used as long as the composition of the present invention exhibits various properties such as excellent adhesive properties aimed at by the present invention. can do.

  For example, film formation, film, sheet, container, and tube-shaped laminates by inflation molding by coextrusion technique, T-die film molding, blow molding, etc .; sequential extrusion lamination, sandwich extrusion lamination, film by coextrusion lamination, sheet Forming the laminated body in the form; Or, this is further stretched to obtain a stretched product; or molding by vacuum molding, pressure molding, etc .; the resin and the composition of the present invention forming a melted adhesive layer in the mold Various known molding techniques such as co-injection molding in which a product is injected with a time lag; a co-injection molded product is further stretch-molded; and the like can be employed.

  Hereinafter, the present invention will be described more specifically with reference to examples.

  In the following, evaluation methods for various physical properties and characteristics are as follows.

<Number of terminal vinyl groups per 1000 carbons>
^{By 13} C-NMR, a solution obtained by dissolving 390 mg of a terminal vinyl-modified propylene polymer in 2.6 ml of a solvent (o-dichlorobenzene: bromobenzene-d ₅ = 8: 2) was used as a measurement sample, and as a spectrometer. Quantification was performed under the following conditions using NMR AVANCE III cryo-400 MHz manufactured by Bruker BioSpin Corporation.
Flip angle: 90 degrees Pulse interval: 15 seconds Resonance frequency: 100 MHz
Integration count: 512 times Observation area: -20ppm to 189ppm

The vinyl group content of the formula (7) of the terminal vinyl-modified propylene polymer represented by the following formula (16) is the position of * 3 and * 4 in the following formula (16) in ¹³ C-NMR measurement, respectively. Since peaks derived from carbon atoms appear in the vicinity of 111.2 ppm and 144.5 ppm, the peak is derived by quantifying this peak, and the terminal vinyl-modified propylene polymer represented by the following formula (17) is used. As for the amount of terminal olefin group in formula (8), peaks derived from carbon atoms at positions * 5 and * 6 in the following formula (17) appear near 115.5 ppm and 137.6 ppm, respectively. The peak was determined by quantification.

<Mm fraction>
Calculation was performed by ¹³ C-NMR under the same conditions as the number of terminal vinyl groups per 1000 carbons.

<Quantification of modified group in terminal-modified propylene polymer>
^Using a solution obtained by dissolving 390 mg of a terminal-modified propylene-based polymerization pair in 2.6 ml of o-dichlorobenzene-d ₄ by ¹ H-NMR, a Bruker BioSpin Corporation AVANCEIII cryo-400 MHz spectrometer was used. And a peak derived from a hydrogen atom of a double bond portion at the position of * 2 in the following formula (I-1), which appears near 5.60 ppm and 5.75 ppm at a measurement temperature of 120 ° C .; The amount of the terminal-modified group (1) is obtained by quantifying the modification rate based on the ratio of the terminal vinyl group of the starting terminal vinyl-modified propylene polymer appearing in the vicinity of 15 ppm and 5.35 ppm to the peak derived from the hydrogen atom of the terminal vinyl group. It was.

<Quantification of olefin unit (2) in terminal-modified propylene polymer>
In the quantification of the modifying group (1), the peak derived from the hydrogen atom of the double bond portion at the position of * 2 in the formula (I-1) appearing near 5.60 ppm and 5.75 ppm is quantified. Thus, the unit of the formula (2) was quantified.

<Molecular weight and molecular weight distribution of terminal vinyl-modified propylene polymer>
Molecular weight (Mn) and molecular weight distribution (Mw / Mn) were measured by GPC under the following conditions.
Equipment: GPC manufactured by Waters (ALC / GPC, 150C)
Detector: MIRAN, 1A, IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml
Calibration sample: monodisperse polystyrene

<Molecular weight and molecular weight distribution of terminal-modified propylene polymer>
Molecular weight (Mn) and molecular weight distribution (Mw / Mn) were measured by GPC under the following conditions.
Apparatus: GPCV 2000 (2) manufactured by Waters
Detector: RI detector (built-in device)
Column: TSKgel GMH6-HT (7.5 mm ID × 30 cm) (four)
Mobile phase solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 135 ° C
Flow rate: 0.5 ml / min Injection volume: 0.05% by weight × 515.5 μl
Calibration sample: monodisperse polystyrene

<Adhesive properties>
The adhesive properties described below were evaluated using ethylene / vinyl alcohol copolymers (EVOH, trade names Soarnol DT2904 and AT4403 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) as resin layers to be adhered.
First, by using a hot press molding machine (MiniTestPress manufactured by TOYO SEIKI) under the conditions of a temperature of 200 ° C., a pressure of 15 MPa, and a pressing time of 2 minutes (2 minutes heating → 2 minutes pressing → 2 minutes cooling) A sheet (A sheet) made of a resin composition having a length of 30 mm, a width of 30 mm, and a thickness of 0.5 mm was obtained. Each of the two types of EVOH, which are raw materials for the resin layer to be bonded, was press-molded under the same conditions to obtain an EVOH sheet (B sheet) of the above size.
Next, the A sheet is positioned on the left side, the B sheet is positioned on the right side, and both sheets are arranged side by side so that they do not overlap, and then the left A sheet is moved in the direction of the right B sheet, The A sheet overlapped with the 1 cm width on the right side from above the B sheet. A hot press molding machine was used to heat the parts where the two sheets overlap at a temperature of 200 ° C., a pressure of 15 MPa, and a press time of 2 minutes, and the two sheets were adhered (6 minutes heating → 2 minutes). Press → 2 minutes cooling).
The laminated portion of the obtained test piece was repeatedly imparted with a bend of about ± 10 mm in the vertical direction of the sheet surface, and the adhesiveness was evaluated by whether or not peeling occurred on the bonding surface. The bending in the vertical direction was performed by moving up and down twice per second, and was bent a total of 10 times.

[Production Example 1: Production of terminal vinyl-modified propylene polymer (E-1)]
According to the method described in Example 10 of JP-A-2009-299045, the catalyst was prepared and prepolymerized.

The 3 L autoclave was dried well by circulating nitrogen under heating, and then the inside of the tank was replaced with propylene and cooled to room temperature. After charging 2.86 mL of a heptane solution of triisobutylaluminum (142 mg / mL) and introducing 750 g of liquid propylene, the temperature was raised to 75 ° C.
Then, 200 mg of the prepolymerized catalyst as a weight excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon, and polymerization was started. After maintaining at 75 ° C. for 1 hour, unreacted propylene was quickly purged to terminate the polymerization, and 233 g of a terminal vinyl-modified propylene polymer (E-1) was obtained.

[Production Example 2: Production of terminal vinyl-modified propylene polymer (E-2)]
A terminal vinyl-modified propylene polymer (E-2) was obtained in the same manner as in Production Example 1 except that the reaction temperature was 90 ° C. and the reaction time was 2 hours.

  Table 1 shows the analysis results of the obtained terminal vinyl-modified propylene polymers (E-1) and (E-2).

[Example 1]
To a separable flask to which a reflux tube having an internal volume of 2 liters was bonded, 100 g of the terminal vinyl-modified propylene polymer (E-1) produced in Production Example 1 and the terminal vinyl-modified propylene polymer (E-1) 1000 equivalents of 196 g of maleic anhydride and a weight equivalent to 1.50% by weight of the total weight of terminal vinyl-modified propylene polymer (E-1) and maleic anhydride (Ciba Japan) Co., Ltd. Product name Irganox 1010) and 1.50% by weight of phosphorus-based heat stabilizer (Ciba Japan Co., Ltd. product name Irgafos 168) are added, 500 mL of o-dichlorobenzene is added as a solvent, and nitrogen is added. The reaction was carried out for 100 hours under conditions of a pressure of 101.3 KPa and a reaction temperature of 175 ° C. in an atmosphere. The same amounts of Irganox 1010 and Irgafos 168 were added to the reaction vessel 30 hours and 70 hours after the start of the reaction. After completion of the reaction, 2 L of acetone was added dropwise to the reaction solution to obtain a crude terminal-modified propylene polymer.

The obtained crude terminal-modified propylene polymer was dissolved in 0.3 L of o-dichlorobenzene heated to 175 ° C. in a nitrogen atmosphere, and then reprecipitated using 2 L of acetone as a poor solvent in a nitrogen atmosphere. Was purified at 50 ° C. and filtered to obtain a terminal-modified propylene polymer. The reprecipitation was performed twice. Thereafter, the obtained terminal-modified propylene polymer was dried under reduced pressure at 50 ° C. and 1 Torr to obtain a white terminal-modified propylene polymer (B-1).
As a result of ¹ H-NMR measurement, no peak derived from the terminal olefin moiety of the terminal vinyl-modified propylene polymer (E-1) was observed, and 100% of the terminal olefin part was modified with maleic anhydride. It was confirmed that Moreover, the said terminal modification group (1) was a succinic anhydride group substantially.
The unreacted maleic anhydride content in the terminal-modified propylene polymer (B-1) determined by FT-IR was 0.001% by weight.
Table 2 shows other physical properties of the terminal-modified propylene polymer (B-1).

[Reference Example 1]
In Example 1, except that an antioxidant and a phosphorus-based heat stabilizer were not added, production, purification, and drying were carried out under the same conditions and methods as in Example 1 to obtain a pale yellow solid. When this solid was re-precipitated, the precipitation of the polymer was extremely poor and it was in the state of an emulsion, and the product was finely dispersed in the filtrate. Even after filtration, many passed through the filter medium, and the product collection efficiency was poor. Since the obtained product was also brittle and the antioxidant and the phosphorus-based heat stabilizer were not allowed to coexist, a large amount of molecular weight was reduced due to thermal decomposition with respect to the growth molecule during production, and as a result of GPC measurement, Mn 19000 was sufficient. It was not high molecular weight. Moreover, as a result of analyzing and analyzing the obtained product by ¹ H-NMR spectroscopy, it became a complicated spectrum pattern and the details of each peak were difficult. However, since the signal in the vicinity of 4.9 ppm to 5.3 ppm where the peak derived from the internal olefin appears is significantly larger than usual, it strongly suggests that the internal olefin contributing to gelation and the like increases. It was. The above ¹ H-NMR measurement was carried out using a solution prepared by dissolving 500 mg of the purified product in 2.7 ml of deuterated o-dichlorobenzene at 130 ° C., and Bruker BioSpin Corp. AVANCEIII cryo- A 400 MHz spectrometer was used under known general conditions except for a temperature condition of 120 ° C.

[Comparative Example 1]
To the separable flask to which a reflux tube having an internal volume of 0.3 liter is coupled, 60 g of the terminal vinyl-modified propylene polymer (E-2) and the terminal vinyl-modified propylene polymer (E-2) produced in Production Example 2 500 equivalents of 358 g of maleic anhydride and a weight of antioxidant equivalent to 1.50% by weight of the total weight of the terminal vinyl-modified propylene polymer (E-2) and maleic anhydride (Ciba Japan) Co., Ltd. Product name Irganox 1010) and phosphorus heat stabilizer (Ciba Japan Co., Ltd. product name Irgafos 168) with a weight equivalent to 1.50% by weight was added, and 300 mL of o-dichlorobenzene was added as a solvent. Production, purification and drying were carried out under the same conditions and method as in Example 1 to obtain a white terminal-modified propylene polymer (B-2).
As a result of ¹ H-NMR measurement, succinic anhydride groups derived from maleic anhydride were introduced into 96% of the terminal olefin sites of the terminal vinyl-modified propylene polymer (E-2).
Table 2 shows other physical properties of the resulting terminal-modified propylene polymer (B-2).

[Example 2]
Using a Brabender kneader (labor plast mill, manufactured by TOYO SEIKI), the composition was produced by kneading on a 40 g scale as the total amount of the starting materials. Specifically, a terminal-modified propylene polymer (B-1) and a commercially available polypropylene (Novatec PP FY4 manufactured by Nippon Polypro Co., Ltd.) are added, and in addition, an antioxidant (Ciba Japan Co., Ltd., product name Irganox 1010). And a phosphorus-based heat stabilizer (Ciba Japan Co., Ltd., product name Irgafos 168) were added and kneaded to obtain the composition (S-1) of the present invention. The terminal modified propylene polymer (B-1) has a terminal succinic anhydride group in the composition in an amount of 0.020% by weight, and an antioxidant and a phosphorous heat stabilizer in the composition in an amount of 0.10% by weight, respectively. It was made to be. The kneading temperature was 230 ° C., the kneading stirring rotation speed was 150 rpm, and kneading was performed for 5 minutes.

  As a result of evaluating the adhesive properties of the composition (S-1), peeling and the like were not observed on the adhesive surface even though the terminal succinic anhydride group was a low concentration of 0.020% by weight in the composition. It was not seen and it was confirmed that it has excellent adhesive properties. In addition, fish eyes and the like due to gelation were not observed on the adhesive surface.

[Example 3]
The terminal succinic anhydride group possessed by the terminal-modified propylene polymer (B-1) is changed to 0.040% by weight in the composition by changing the proportion of the terminal-modified propylene polymer (B-1) and commercially available polypropylene. A composition (S-2) was obtained by kneading under the same conditions and method as in Example 2 except that the composition was included.

  As a result of evaluating the adhesive properties with respect to this composition (S-2), it was confirmed that no peeling or the like was observed on the adhesive surface and the adhesive properties were excellent. In addition, fish eyes and the like due to gelation were not observed on the adhesive surface.

[Example 4]
The terminal succinic anhydride group of the terminal-modified propylene polymer (B-1) was changed to 0.10% by weight in the composition by changing the proportion of the terminal-modified propylene polymer (B-1) and commercially available polypropylene. A composition (S-3) was obtained by kneading under the same conditions and method as in Example 2 except that it was included.

  As a result of evaluating the adhesive properties of this composition (S-3), it was confirmed that the adhesive surface had excellent adhesive properties with no peeling or the like. In addition, fish eyes and the like due to gelation were not observed on the adhesive surface.

[Reference Example 2]
The terminal succinic anhydride group possessed by the terminal-modified propylene polymer (B-1) was changed to 0.010% by weight in the composition by changing the proportion of the terminal-modified propylene polymer (B-1) and commercially available polypropylene. A composition (S-4) was obtained by kneading under the same conditions and method as in Example 2 except that the composition was included.

  As a result of evaluating the adhesive properties of this composition (S-4), peeling was observed on the adhesive surface. From this result, it is surmised that when the amount of terminal succinic anhydride groups in the composition is small, the number of bonds involving terminal succinic anhydride groups contributing to adhesion decreases, and good adhesive properties cannot be obtained. In addition, fish eyes and the like due to gelation were not observed on the adhesive surface.

[Comparative Example 2]
In Example 2, the terminal-modified propylene polymer (B-2) was added instead of the terminal-modified propylene polymer (B-1), and the amount of terminal succinic anhydride groups contained in the composition was 0.040. A composition (S-5) was obtained by kneading under the same conditions and method as in Example 2 except that the weight% was used.
As a result of evaluating the adhesive properties of this composition (S-5), peeling was observed on the adhesive surface. As a result, since the molecular weight of the terminal-modified propylene polymer (B-2) contained in the resin composition is small, particularly the propylene molecular chain length in the terminal-modified propylene polymer (B-2) is short, the resin Due to the fact that the dilute resin contained in the composition does not have sufficient binding force due to the hydrophobic bond with the polypropylene resin, and the terminal-modified propylene polymer (B-2) molecule has escaped from the composition simultaneously with peeling. Inferred. Note that fish eyes and the like due to gelation were not observed on the adhesive surface.

[Comparative Example 3]
The terminal succinic anhydride group of the terminal-modified propylene polymer (B-2) is changed to 0.010% by weight in the composition by changing the proportion of the terminal-modified propylene polymer (B-2) and commercially available polypropylene. A composition (S-6) was obtained by kneading under the same conditions and method as in Comparative Example 2 except that the composition was included.
As a result of evaluating the adhesive properties of this composition (S-6), peeling was observed on the adhesive surface. This result shows that the terminal-modified propylene polymer (B) contained in the resin composition as in Comparative Example 2, in addition to the low concentration of the terminal succinic anhydride group of 0.010 wt% in the composition. It is inferred that the molecular weight of -2) is small. Note that fish eyes and the like due to gelation were not observed on the adhesive surface.

[Comparative Example 4]
The terminal succinic anhydride group of the terminal-modified propylene polymer (B-2) is changed to 0.50% by weight in the composition by changing the proportion of the terminal-modified propylene polymer (B-2) and commercially available polypropylene. A composition (S-7) was obtained by kneading under the same conditions and method as in Comparative Example 2 except that the composition was included.

  As a result of evaluating the adhesive properties of this composition (S-7), peeling was observed on the adhesive surface. That is, although the terminal succinic anhydride group was a high concentration of 0.50% by weight in the composition, a sufficient adhesion effect was not observed and peeling was observed. This is presumed to be due to the low molecular weight of the terminal-modified propylene polymer (B-2) contained in the resin composition described in Comparative Example 2, and in order to develop excellent adhesive properties, It is shown that the molecular weight of the terminal vinyl-modified propylene polymer molecule contained in the resin composition is important. In addition, fish eyes and the like due to gelation were not observed on the adhesive surface.

  The above results are summarized in Table 3.

Claims (9)

It has structural units represented by the following (1) to (3), has a number average molecular weight of 52,000 or more and 1,000,000 or less, and binds to one molecular terminal among all the modifying groups in one molecule. A modified propylene polymer composition comprising, as a main component, a terminal-modified propylene polymer in which the ratio of the modified group is 60% or more and 100% or less.

(Wherein R ₁ represents a modifying group)

(In the formula, R ₂ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.)

  In Claim 1, the structural unit represented by said (1)-(3) is directly couple | bonded in the order of (1)-(2)-(3) in the molecular terminal of the said terminal modified propylene polymer. A modified propylene polymer composition characterized by comprising:   3. The modified propylene polymer composition according to claim 1, wherein the content of the modifying group in the terminal-modified propylene polymer is 0.010 wt% or more and 0.30 wt% or less.   The modified group according to any one of claims 1 to 3, wherein the modifying group is derived from one or more modifying agents selected from unsaturated carboxylic acids and anhydrides thereof and derivatives thereof. Modified propylene polymer composition.   In any 1 item | term of the Claims 1 thru | or 4, the said terminal modified propylene polymer is a modifier in presence of antioxidant with the propylene polymer which has the structural unit of the said Formula (2) in the terminal. A modified propylene polymer composition obtained by reacting under heating conditions.   A composite resin composition comprising a resin other than the terminal-modified propylene polymer mixed with the modified propylene polymer composition according to any one of claims 1 to 5.   The composite resin composition according to claim 6, wherein the content of the modifying group in the composition is 0.015 wt% or more and 0.20 wt% or less.   An adhesive resin composition comprising the composite resin composition according to claim 6 or 7.   A laminate comprising the adhesive resin composition layer according to claim 8.