JP2006290983A - Carbodiimide-modified aromatic adhesive and layered product using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a carbodiimide-modified aromatic polymer adhesive by which the reduction of bonding force between a polar resin and an aromatic polymer is suppressed; and to provide a layered product comprising the polymer composition and having excellent interlaminar bonding force. <P>SOLUTION: The adhesive (D) is obtained by reacting a polyolefin (A) having a group reactive with a carbodiimide group, with a carbodiimide group-containing compound (B). The multi-layered product is obtained by bonding the polar resin (F) with the aromatic polymer (G) and/or a polyolefin (H) through the adhesive (D), or two or more kinds of the polar resins (F) through the adhesive (D). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel adhesive and a laminate using the same.

  More specifically, the present invention relates to an adhesive (D) obtained by reacting an aromatic polymer (A) having a group that reacts with a carbodiimide group and a carbodiimide group-containing compound (B), and a polarity using the same. The present invention relates to a laminate of resin (F) and aromatic polymer (G) and / or polyolefin (H).

  Adheres a graft-modified ethylene / α-olefin random copolymer composition grafted with an unsaturated carboxylic acid or its derivative to a polar resin that is difficult to adhere to polyolefin, such as polyester such as polyethylene terephthalate or polycarbonate. It is already known to be used as a composition for medical use (see Patent Documents 1 and 2). Although these ethylene-based modified resin compositions have excellent adhesiveness, for example, since a laminate with an aromatic polymer such as polystyrene does not have adhesive strength, an aromatic polymer that can be bonded to polyester and polycarbonate is used. Conventionally, an adhesive composition has been desired.

  Styrene-based molded products include food cups such as jelly cups and beverage cups, and are suitable as food containers if they can be laminated with glossy and oxygen gas barrier polyester resins.

  For the purpose of improving the adhesive strength, an adhesive resin composition comprising a modified aromatic resin composition is already known. However, these adhesives are not satisfactory for use as adhesives because of the insufficient reactivity of the modifying groups.

JP 61-270155 A Japanese Patent Laid-Open No. Sho 62-158043

  The subject of this invention is providing the laminated body excellent in the interlayer adhesive force which consists of a carbodiimide modified | denatured aromatic polymer adhesive agent which is excellent in adhesive force, and the said polymer composition.

  The present inventor has intensively studied and reacting an aromatic polymer (A) having a group that reacts with a carbodiimide group and a carbodiimide group-containing compound (B), thereby efficiently performing a carbodiimide chain and an aromatic polymer chain. Were able to produce an adhesive (D) having the same chain, and the resulting adhesive was found to have improved adhesive strength, leading to the completion of the present invention.

  That is, the present invention is an adhesive obtained by reacting an aromatic polymer (A) having a group that reacts with a carbodiimide group and a carbodiimide group-containing compound (B).

  In addition, the present invention provides the polar resin (F) and the aromatic polymer (G) and / or polyolefin (H) through the adhesive (D), or two or more polar resins through the adhesive (D). It is a multilayer laminated body formed by bonding (F).

  The carbodiimide-modified polyolefin adhesive (D) of the present invention is a composition excellent in adhesiveness between the polar resin (F) and the aromatic polymer (G) or adhesiveness with the polar resin (F). . According to the carbodiimide-modified aromatic polymer adhesive (D) of the present invention, a laminate having excellent interlayer adhesion can be obtained.

  Hereinafter, the present invention will be described in more detail.

  The carbodiimide-modified aromatic adhesive (D) of the present invention is an adhesive obtained by reacting an aromatic polymer (A) having a group that reacts with a carbodiimide group and a carbodiimide group-containing compound (B). Yes, it is also possible to use an unmodified polymer as the reaction diluent.

  Each component will be described below.

Aromatic polymer having a group that reacts with carbodiimide group (A)
The aromatic polymer (A) having a group that reacts with a carbodiimide group used in the present invention can be obtained by introducing a compound (a) having a group that reacts with a carbodiimide group into the aromatic polymer.

  Examples of the compound (a) having a group that reacts with a carbodiimide group include compounds having a group having an active hydrogen that is reactive with a carbodiimide group. Specifically, a carboxylic acid, an amine, an amide, an imine, an alcohol, A compound having a group derived from thiol or the like. In addition, since carbodiimide also serves as an electrophilic reagent, a compound having a group that enables an electrophilic reaction can be used. Among these, compounds having a group derived from carboxylic acid and imines are preferably used, and among them, unsaturated carboxylic acid, imine and / or derivatives thereof are particularly preferable. In addition to a compound having a group having an active hydrogen, a compound having a group that can be easily converted into a group having an active hydrogen by water or the like can be preferably used. Specifically, it has an epoxy group or a glycidyl group. Compounds. In the present invention, the compound (a) having a group that reacts with a carbodiimide group may be used alone or in combination of two or more.

  In the present invention, when an unsaturated carboxylic acid and / or derivative thereof is used as the compound (a) having a group that reacts with a carbodiimide group, an unsaturated compound having at least one carboxylic acid group and an unsaturated compound having at least one carboxylic anhydride group are used. Saturated compounds and derivatives thereof can be exemplified, and examples of the unsaturated group include vinyl group, vinylene group, unsaturated cyclic hydrocarbon group and the like. Specific compounds include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept-2 -Unsaturated carboxylic acids such as ene-5,6-dicarboxylic acid, or acid anhydrides or derivatives thereof (for example, acid halides, amides, imides, esters, etc.). Specific examples of the compound include maleenyl chloride, maleenylimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid. Acid anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene-5,6 -Dicarboxylate dimethyl, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate, aminopropyl methacrylate and the like.

  When an unsaturated carboxylic acid and / or derivative thereof is used as the compound (a) having a group that reacts with a carbodiimide group, it can be used alone or in combination of two or more. it can. Among these, maleic anhydride, (meth) acrylic acid, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride , Hydroxyethyl (meth) acrylate, glycidyl methacrylate, and aminopropyl methacrylate are preferred. Furthermore, it is a dicarboxylic anhydride such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride. It is particularly preferred.

  As a method for introducing the compound (a) having a group that reacts with a carbodiimide group into an aromatic polymer, a well-known method can be adopted. For example, a reaction with a carbodiimide group in an aromatic polymer main chain is possible. Examples thereof include a method of graft copolymerizing a compound (a) having a group capable of radical polymerization, a method of radical copolymerizing a compound (a) having a group that reacts with an aromatic polymer and a carbodiimide group, and the like.

  Hereinafter, the case of graft copolymerization and the case of radical copolymerization will be described specifically.

<Graft copolymerization>
The aromatic polymer (A) having a group that reacts with a carbodiimide group in the present invention is obtained by graft copolymerization of a compound (a) having a group that reacts with a carbodiimide group on the aromatic polymer main chain. Is possible.

(Aromatic polymer main chain)
The polymer used as the aromatic polymer main chain is a polymer containing aromatic hydrocarbon such as styrene as a main component, and preferably styrene. About these monomers, you may use individually by 1 type or 2 or more types. The content of the aromatic hydrocarbon is usually 80 mol% or less, preferably 60 mol% or less, more preferably 55 mol% or less. In the present invention, an aromatic hydrocarbon homopolymer or copolymer can be preferably used.

The density of the aromatic polymer used for graft modification is usually 0.85 to 1.1 g / cm ³ , preferably 0.86 to 1.05 g / cm ³ , and more preferably 0.88 to 1.03 g / cm ³ . a ^3, 230 ° C. by ASTM D1238, a melt flow rate of 2.16kg load (MFR) is usually 0.01 to 500 g / 10 min, preferably 0.05~200g / 10 min, more preferably 0.1 ~ 100 g / 10 min. If the density and MFR are in this range, the density and MFR of the graft copolymer after modification are also comparable, so that handling is easy.

  The number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of polyolefin used for graft modification is preferably 5,000 to 500,000, more preferably 1,000 to 10,000. When the average molecular weight (Mn) is within this range, the handling is excellent. The number average molecular weight can be determined in terms of polystyrene.

  The production of the aromatic polymer as described above can be performed by any conventionally known method. For example, the polymerization can be performed using a titanium-based catalyst, a vanadium-based catalyst, a metallocene catalyst, or the like. In addition, the aromatic polymer used for graft modification may be in the form of either a resin or an elastomer, and both isotactic and syndiotactic structures can be used, and there is no particular restriction on stereoregularity. . Commercially available resins can be used as they are.

(Graft polymerization method)
When the aromatic polymer (A) having a group that reacts with the carbodiimide group used in the present invention is obtained by graft copolymerization, a group that reacts with the carbodiimide group is added to the aromatic polymer that becomes the graft main chain. Graft copolymerization is carried out in the presence of a radical initiator of the compound having, and if necessary, other ethylenically unsaturated monomers, imino groups and the like.

  A method for grafting a compound having a group that reacts with a carbodiimide group onto an aromatic polymer main chain is not particularly limited, and a conventionally known graft polymerization method such as a solution method or a melt-kneading method can be employed.

<Radical copolymerization>
The aromatic polymer (A) having a group that reacts with a carbodiimide group in the present invention can also be obtained by radical copolymerization of a compound (a) having a group that reacts with an aromatic monomer and a carbodiimide group. is there. As the aromatic monomer, it is possible to adopt the same aromatic monomer as used in the case of forming the aromatic polymer (A) to be the graft main chain, and it reacts with a carbodiimide group. The compound (a) having a group is also as described above.

  A method for copolymerizing a compound having a group that reacts with an aromatic monomer and a carbodiimide group is not particularly limited, and a conventionally known radical copolymerization method can be employed.

(Method for producing aromatic polymer (A) having a group that reacts with carbodiimide group)
The content of the compound (a) having a group reactive with a carbodiimide group in the aromatic polymer (A) having a group reactive with a carbodiimide group used in the present invention is usually 0.1 to 13% by weight, Preferably it is 0.1 to 12 weight%, More preferably, it is 0.1 to 10 weight%. When the content of the compound (a) having a group that reacts with a carbodiimide group exceeds the above range, it may be difficult to produce an adhesive (D) by crosslinking with the carbodiimide group-containing compound (B). .

  On the other hand, in the present invention, when the content of the compound (a) having a group that reacts with a carbodiimide group in the aromatic polymer (A) having a group that reacts with a carbodiimide group is small, the adhesive (D) Although it can be manufactured, the bonding portion between the carbodiimide group-containing compound (B) and the aromatic polymer (A), which is the skeleton of the adhesive (D), is reduced. Power tends to be small.

  In order to prevent crosslinking, the lower the number average molecular weight of the aromatic polymer (A) having a group that reacts with a carbodiimide group, the more the number of moles of the compound (a) having a group that reacts with a carbodiimide group) The molar ratio of / (aromatic polymer (A) moles of molecular chain) is preferably small. That is, the compound (a) having a group that reacts with a carbodiimide group is present in a state close to a single number on the molecular chain of the aromatic polymer (A) having a group that reacts with a carbodiimide group. In this case, when the carbodiimide group (N = C = N) of the carbodiimide group-containing compound (B) reacts with the compound (a) having a group that reacts with the carbodiimide group, it means that the carbodiimide group can be bonded without crosslinking or gelation. is doing.

  In the present invention, by controlling the number average molecular weight (Mn) of the aromatic polymer (A) having a group that reacts with a carbodiimide group and the content of the compound (a) having a group that reacts with a carbodiimide group. In the production of the adhesive (D), cross-linking occurs, and the production stability does not decrease. In addition, when the adhesive (D) is used to form a laminate, a sufficient adhesive force can be obtained. That is, in the present invention, the aromatic polymer (A) having a group that reacts with a carbodiimide group preferably satisfies the following formula (1).

0.1 <Mn / (100 * f / M) <6 (1)
(Where
f: Formula weight (g / mol) of the compound (a) having a group that reacts with a carbodiimide group
M: content (% by weight) of compound (a) having a group that reacts with a carbodiimide group
Mn: Number average molecular weight of the aromatic polymer (A). )
Further, from the viewpoint of production stability of not being crosslinked, it is more preferably a range satisfying the following formula (2), and most preferably a range satisfying the formula (3).

0.3 <Mn / (100 * f / M) <3 (2)
0.5 <Mn / (100 * f / M) <2 (3)
When the relationship between the number average molecular weight (Mn) of the aromatic polymer (A) having a group that reacts with a carbodiimide group and the compound (a) having a group that reacts with a carbodiimide group is within the above range, the adhesive (D) When manufacturing, it becomes possible to manufacture stably without crosslinking.

  In the present invention, when the aromatic polymer (A) having a group that reacts with a carbodiimide group is obtained by graft polymerization, the compound having a group that reacts with a carbodiimide group is present on the molecular chain of the polyolefin (A). The closer to the singular number, that is, the lower the number in the above formula, the more the crosslinking can be suppressed.

  The number average molecular weight can be determined by a general molecular weight measurement method for polymers such as GPC method, light scattering method, low angle light scattering photometry method, vapor pressure osmotic pressure method, membrane osmotic pressure method.

  The melt flow rate (MFR) at 230 ° C. under a load of 2.16 kg according to ASTM D1238 of the aromatic polymer (A) having a group that reacts with the carbodiimide group used in the present invention is usually 0.01 to 500 g / 10 min. , Preferably 0.05 to 100 g / 10 min. When in the above range, the adhesive strength is excellent when the adhesive (D) is formed.

The density of the aromatic polymer (A) having a group that reacts with a carbodiimide group is usually 0.8 to 1.03 g / cm ³ , preferably 0.90 to 1.0 g / cm ³ , and more preferably 0. .91 to 0.94 g / cm ³ .

  As the resin to be modified as the aromatic polymer (A), a styrene elastomer is desirable, and styrene / ethylene / butylene / styrene block copolymer (hereinafter abbreviated as SEBS), styrene / butadiene / butylene / styrene block copolymer ( SBBS, styrene / isoprene / styrene block copolymer (hereinafter abbreviated as SIS), and styrene / butadiene / styrene block copolymer (hereinafter abbreviated as SBS) are particularly desirable. As an aromatic polymer (A) used for this invention, these 1 type may be individual, or 2 or more types may be used.

Carbodiimide group-containing compound (B)
The carbodiimide group-containing compound (B) used in the present invention is a polycarbodiimide having a repeating unit represented by the following general formula (4).

-N = C = N-R1-(4)
[Wherein R1 represents a divalent organic group]
Although the synthesis method of polycarbodiimide is not specifically limited, For example, polycarbodiimide can be synthesize | combined by making organic polyisocyanate react in presence of the catalyst which accelerates | stimulates the carbodiimidization reaction of an isocyanate group.

  The number average molecular weight (Mn) in terms of polystyrene determined by gel permeation chromatography (GPC) of the carbodiimide group-containing compound (B) used in the present invention is usually 400 to 500,000, preferably 1,000 to 10,000. More preferably, it is 2,000 to 4,000. When the number average molecular weight (Mn) is in this range, it is preferable because the adhesive strength of the adhesive (D) is excellent.

  The carbodiimide group-containing compound (B) used in the present invention may contain monocarbodiimide in polycarbodiimide, or a single compound or a mixture of a plurality of compounds can be used.

  A commercially available carbodiimide group-containing compound can be used as it is. Examples of commercially available carbodiimide group-containing compounds include Carbodilite HMV-8CA and LA1 manufactured by Nisshinbo Industries, Ltd.

  The carbodiimide group content in the carbodiimide group-containing compound (B) and the obtained compatibilizer (C) can be measured by C-NMR, IR, titration method, etc., and can be grasped as a carbodiimide equivalent. It is possible to observe a peak at 130 to 142 ppm in C-NMR and 2130 to 2140 cm-1 in IR.

Unmodified polymer (C)
Examples of the unmodified polymer (C) used in the present invention are the same as those described in the section of the aromatic polymer main chain in (A) above.

  It can also be selected according to the purpose of use and the type of adherend. For example, styrene-based elastomers are desirable, and styrene / ethylene / butylene / styrene block copolymer (SEBS), styrene / butadiene / butylene / styrene block copolymer (SBBS), styrene / isoprene / styrene block copolymer (SIS), styrene / Butadiene styrene block copolymer (SBS) is particularly desirable.

  Other low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-α olefin copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene Cyclic polyolefins such as copolymers, ethylene-octene copolymers, polybutene-1, poly-4-methyl-1-pentene, poly-3-methyl-1-butene, ethylene-tetracyclododecene copolymers, etc. Is possible. In addition, ethylene-propylene-nonconjugated dienes using a non-conjugated diene such as, for example, 5-ethylidene norbornene, 5-methylnorbornene, 5-vinylnorbornene, dicyclopentadiene, 1,4-pentadiene as the third component. Copolymer rubber (EPDM) or ethylene-propylene-butene terpolymer rubber is also preferably used. These can be used singly or in combination of several kinds.

  Of these, aromatic polymers with a high melting point and high crystallinity are used for use at high temperatures close to 100 ° C. and for adhesive applications such as gasoline and oil that directly contact polyolefin-swelling substances. It is desirable to use it.

  The production of the aromatic polymer as described above can be performed by any conventionally known method. For example, the polymerization can be performed using a titanium-based catalyst, a vanadium-based catalyst, a metallocene catalyst, or the like.

  In addition, the aromatic polymer used for graft modification may be in the form of either a resin or an elastomer, and both isotactic and syndiotactic structures can be used, and there is no particular restriction on stereoregularity. . Commercially available resins can be used as they are.

Adhesive (D)
The adhesive (D) of the present invention is obtained by reacting the aromatic polymer (A) having a group that reacts with a carbodiimide group and the carbodiimide group-containing compound (B), preferably at 230 ° C. or higher. . Specifically, it can be obtained by melt-kneading such as melt modification, but is not limited to this method.

  Below, the example in the case of melt-mixing is shown. The method of reacting the aromatic polymer (A) having a group that reacts with the carbodiimide group and the carbodiimide group-containing compound (B) at 230 ° C. or higher in the presence of the unmodified polymer (C) is particularly limited. The aromatic polymer (A) having a group that reacts with a carbodiimide group, the carbodiimide group-containing compound (B) and the unmodified polymer (C) are simultaneously or sequentially used, for example, a Henschel mixer, a V-type blender, a tumbler. It can be obtained by charging into a blender, ribbon blender, etc. and kneading, and then melt-kneading with a single screw extruder, multi-screw extruder, kneader, Banbury mixer or the like. Among these, it is preferable to use an apparatus excellent in kneading performance such as a multi-screw extruder, a kneader, and a Banbury mixer because a polymer composition in which each component is dispersed and reacted more uniformly can be obtained.

  The aromatic polymer (A) having a group that reacts with a carbodiimide group, the carbodiimide group-containing compound (B), and the unmodified polymer (C) are mixed in advance and then supplied from the hopper, and some components are supplied from the hopper. In addition, it is possible to adopt any method of supplying other components from a supply port installed in an arbitrary portion between the vicinity of the hopper portion and the tip of the extruder.

  The temperature at the time of melt kneading the above components can be reacted at the highest melting point or higher among the melting points of the respective components to be mixed. Specifically, it is usually 180 to 300 ° C, preferably 230 to 280 ° C. More preferably, melt kneading is performed in the range of 250 to 270 ° C.

  The adhesive (D) of the present invention is excellent in fluidity at 230 ° C. The melt flow rate (MFR) at 230 ° C. and a load of 2.16 kg of the adhesive (D) of the present invention is usually 0.01 to 100 g / 10 minutes, preferably 0.1 to 50 g / 10 minutes, more preferably 1 It is in the range of ˜20 g / 10 minutes. Within such a range, high adhesiveness is obtained and moldability is good, which is preferable.

  In the production of the adhesive (D) of the present invention, the compounding amount of the carbodiimide group-containing compound (B) is the same as that of the aromatic polymer (A) having a group that reacts with the carbodiimide group and the carbodiimide group-containing compound (B). The content of the carbodiimide group is usually 0.5 to 50 mmol, preferably 1 to 20 mmol, more preferably 2 to 10 mmol with respect to 100 g of the adhesive (D) reacted in the presence of the modified polymer (C). If the carbodiimide group content is too small, there are too few reaction points per unit area of the adhesive surface with the polar resin that should exhibit adhesiveness, so that the adhesive force is not expressed, and if it is too much, the molding processability decreases, Adhesive strength also decreases.

  Furthermore, in the adhesive (D) of the present invention, control of the reaction between the group (a-2) that reacts with the carbodiimide group in the aromatic polymer (A) and the carbodiimide group in the carbodiimide group-containing compound (B). Is the weight. The progress of the reaction between the group (a) reacting with the carbodiimide group in the aromatic polymer (A) having a group that reacts with the carbodiimide group and the carbodiimide group in the carbodiimide group-containing compound (B) is, for example, It is possible to investigate by this method.

  The aromatic polymer (A) having a group that reacts with the carbodiimide group of the present invention, and the present invention in which the aromatic polymer (A) having a group that reacts with a carbodiimide group and the carbodiimide group-containing compound (B) are reacted. After each of the hot press sheets of the adhesive (D) is prepared, an infrared absorption chart is measured using an infrared absorption analyzer. From the obtained chart, the aromatic polymer (A) having a group that reacts with a carbodiimide group and the peak intensity of the compound (a) having a group that reacts with a carbodiimide group in the adhesive (D) of the present invention. The absorbance before and after the reaction with the carbodiimide group-containing compound (B) in the absorbance of the absorption band (1790 cm-1 when maleic anhydride is used) is compared, and the reaction rate can be calculated using the following formula.

Reaction rate (%) = X / Y × 100
X = difference in strength of groups reacting with carbodiimide groups (before reaction (A) -after reaction (C))
Y = strength of group reacting with carbodiimide group before reaction (A)

  The reaction rate calculated | required with the said method about the adhesive agent (D) of this invention is 40-100% normally, Preferably it is 60-100%, More preferably, it exists in the range of 70-100%.

  It is possible to use two or more aromatic polymers and polyolefins, an aromatic polymer (A) having a group that reacts with the carbodiimide group of the adhesive (D) of the present invention and an unmodified polymer (C). However, these aromatic polymers and polyolefins may use polyolefins having the same composition and the same density, or may use completely different types of polyolefins. For example, (A) modified high density SEBS- (C) high density SEBS, (A) modified low density SEBS- (C) low density SEBS, A) modified high density SEBS- (C) low density SEBS, (A) modified High density SEBS- (C) Ethylene-based elastomers such as ethylene-butene copolymer or ethylene-propylene copolymer, (A) Modified SBBS- (C) Propylene-based elastomers such as propylene-ethylene copolymer, (A) Modified Examples include combinations of ethylene-based elastomers such as SBBS- (C) ethylene-butene copolymer or ethylene-propylene copolymer.

  Moreover, it is also possible to add a well-known process stabilizer, a heat-resistant stabilizer, a heat-resistant aging agent, a filler, etc. to the adhesive agent (D) of this invention in the range which does not impair the objective of this invention.

  In the adhesive (D) of the present invention, the carbodiimide group in the adhesive has reactivity with active hydrogen such as carboxylic acid, amine, imine, amide, alcohol, thiol, etc., and is in the main chain of the aromatic polymer. Since it has a grafted structure, it is effective as an adhesive with the polar resin (F) having active hydrogen.

Adhesive (E)
In the present invention, it is particularly preferable to add a so-called tackifier for the purpose of imparting tackiness. Examples of the substance that imparts tackiness include rosin derivatives, terpene resins, petroleum resins, and hydrides thereof. Among these, hydrogenated terpene resins and hydrogenated petroleum resins are preferable. The tackifier is preferably blended in a proportion of 0 to 30% by weight in the adhesive (D).

In addition, a modified resin having a group that reacts with a carbodiimide group can be blended. For example, maleic acid-modified resin, imine-modified resin, among them maleic acid modified ethylene butene copolymer, maleic acid modified ethylene / propylene copolymer, maleic acid modified ethylene / octene copolymer, Maleic acid-modified styrene-ethylene-butylene-styrene block copolymer (MAH-SEBS), maleic acid-modified styrene-butadiene-butylene-styrene block copolymer (MAH-SBBS), maleic acid-modified styrene-butadiene-styrene block copolymer ( MAH-SBS),
An imine-modified styrene / ethylene / butylene / styrene block copolymer, an imine-modified styrene / butadiene / butylene / styrene block copolymer, and an imine-modified styrene / butadiene / styrene block copolymer are preferable.

Polar resin (F)
The polar resin (F) used in the present invention is a polymer having active hydrogen having reactivity with a carbodiimide group present in the adhesive (D), and is a group derived from carboxylic acid, amine, alcohol, thiol, etc. It is a polymer with Specifically, polyester, polyamide, polylactic acid, polycarbonate, acrylic resin, polyphenylene oxide, polyether sulfone (PES), acrylonitrile-butadiene-styrene copolymer (ABS), ethylene-vinyl alcohol copolymer, polyacetal, etc. Examples of the polyether include polyolefins containing active hydrogen such as a modified polyolefin, an ethylene-ethyl acrylate copolymer, an ethylene-methacrylic acid copolymer, and an ethylene-vinyl acetate copolymer. As polar resin (F) used for this invention, these 1 type may be individual, or 2 or more types may be used.

  Polyesters include polyethylene terephthalate, waste polyethylene terephthalate for recycling, polyethylene naphthalate, polytrimethylene terephthalate, polybutylene terephthalate, amorphous polyester such as glycol-modified polyethylene terephthalate and acid-modified polyethylene terephthalate, polybutylene terephthalate adipate and polyethylene terephthalate succinate. Examples thereof include aromatic polyesters containing biodegradable polyester, polycaprolactone, polyhydroxybutyrate, polyglycolic acid, polylactic acid and other lactic acid resins, and biodegradable polyester resins. Furthermore, liquid crystal polyesters and polyarylates composed of wholly aromatic or semi-aromatic polyesters can be mentioned. Among these, polyethylene terephthalate, polybutylene terephthalate, polylactic acid, and liquid crystal polyester are preferable.

  Examples of polyamides include aliphatic polyamides such as nylon-6, nylon-66, nylon-10, nylon-12, and nylon-46, and aromatic polyamides prepared from aromatic dicarboxylic acids and aliphatic diamines such as nylon-6T and nylon. -9T can be mentioned.

  Examples of the polycarbonate include aromatic bisphenol-type polycarbonates such as bisphenol A polycarbonate and bisphenol F polycarbonate, and aliphatic carbonates such as polyethylene carbonate and polytrimethylene carbonate.

  Examples of the polyacetal include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, polybutyraldehyde, and the like, and polyformaldehyde is particularly preferable.

  As the ethylene-vinyl alcohol copolymer, a copolymer containing 20 to 50 mol%, preferably 25 to 48 mol% of a polymer unit derived from ethylene is desirable. These can be produced by saponifying a corresponding ethylene / vinyl acetate copolymer by a conventional method.

Aromatic polymer (G)
The aromatic polymer (G) used in the present invention is not particularly limited as long as it is aromatic.

  Specific examples include polystyrene (PS), acrylonitrile butadiene styrene copolymer (ABS), acrylonitrile styrene copolymer (AS), acrylonitrile (ethylene propylene diene terpolymer) styrene copolymer (AES), and the like. It is done. As an aromatic polymer (G) used for this invention, these 1 type may be individual, or 2 or more types may be used.

Polyolefin (H)
The polyolefin (H) used in the present invention is not particularly limited as long as it is an olefin type.

  Specifically, low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-α olefin copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, Cyclic rings such as ethylene-hexene copolymer, ethylene-octene copolymer, polybutene-1, poly-4-methyl-1-pentene, poly-3-methyl-1-butene, ethylene-tetracyclododecene copolymer Polyolefins are also possible. In addition, ethylene-propylene-nonconjugated dienes using a non-conjugated diene such as, for example, 5-ethylidene norbornene, 5-methylnorbornene, 5-vinylnorbornene, dicyclopentadiene, 1,4-pentadiene as the third component. Copolymer rubber (EPDM) or ethylene-propylene-butene terpolymer rubber is also preferably used.

  As polyolefin (H) used for this invention, these 1 type may be individual, or 2 or more types may be used.

Multilayer laminate The laminate of the present invention is a multilayer laminate obtained by bonding a polar resin (F) and an aromatic polymer (G) or two or more kinds of polar resins (F) via an adhesive (D). It is a body. Any layer structure may be used as long as this requirement is satisfied.

  The laminate of the present invention may be obtained by any manufacturing method. For example, the polar resin (F) and / or the aromatic polymer (G) in each layer is melted and the melted state is known through blown adhesive, injection molding, extrusion molding or the like via the melted adhesive (D). It can manufacture by laminating | stacking with a shaping | molding method. Further, the polar resin (F) is obtained through a sheet of the polar resin (F) and / or aromatic polymer (G) that has already been processed by extrusion laminating or the like, or an adhesive (D) melted on the film. ) And / or the aromatic polymer (G) can be contacted and pressure-bonded to produce a multilayer laminate.

  As the combination of the laminates of the present invention, polyethylene terephthalate / adhesive / aromatic polymer, polylactic acid / adhesive / aromatic polymer, polycarbonate / adhesive / aromatic polymer, polyethylene terephthalate / adhesive / nylon 6 , Etc., polycarbonate / adhesive / ethylene-vinyl alcohol copolymer / adhesive / aromatic polymer, polylactic acid / adhesive / ethylene-vinyl alcohol copolymer / adhesive / aromatic polymer And 5-layer laminates such as aromatic polymer / adhesive / polyethylene terephthalate / adhesive / aromatic polymer, aromatic polymer / adhesive / liquid crystal polyester / adhesive / aromatic polymer, etc. .

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not restrict | limited at all to these Examples, unless the summary is exceeded.

(Various measurement methods)
In this example and the like, measurement was performed according to the following method.

[Melt flow rate (MFR)]
Measurements were performed according to ASTM D1238 under 230 ° C. and 2.16 load.

[Interlayer adhesion of film]
In a three-layer laminate between polyethylene terephthalate (PET) / adhesive resin / polyethylene terephthalate (PET) and ABS resin, a 180-degree peel test between the PET layer and the intermediate layer (adhesive) was performed in a 23 ° C. atmosphere.

[density]
The density was measured by a density gradient tube after heat-treating the obtained sheet section at 120 ° C. for 1 hour and gradually cooling to room temperature over 1 hour.

(Aromatic polymer used)
Aromatic polymers used in Examples and Comparative Examples are shown below. In addition, unless otherwise indicated, all were prepared by polymerization according to a conventional method.

SEBS-1: SEBS (pellet) manufactured by Asahi Kasei Chemicals Corporation
Product name H1062
(Melt flow rate 0.07, density 890 g / m ³ )
SEBS-2: SEBS (powder) manufactured by Shell Chemical Co., Ltd., trade name Clayton G1652
(Melt flow rate 1.3, density 910 g / m ³ )
M-SEBS-1: maleic acid-modified resin of SEBS-1,
Maleic acid modification amount 0.25% by weight
M-SEBS-2: Maleic acid-modified resin of SEBS-2
Maleic acid modification amount 0.25% by weight
M-SEBS-3: maleic acid-modified resin of SEBS-2
Maleic acid modification amount 1.0 wt%
I-SBBS: Imine-modified SBBS manufactured by Asahi Kasei Chemicals Corporation, product name N503
(Melt flow rate 20, density 910 g / m ³ )

Example 1
<Production of aromatic polymer (A) having a group that reacts with carbodiimide group>
To 100 parts by weight of SEBS-1, maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as MAH) 0.25 part by weight, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (Nippon Yushi Co., Ltd., trade name Perhexa 25B) A solution obtained by dissolving 0.015 part by weight in acetone was dry blended. Thereafter, it was extruded using a twin-screw kneader (manufactured by Nippon Steel Works, TEX-30) at a resin temperature of 250 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 100 g / min. ) The obtained M-SEBS was dissolved in xylene, purified by reprecipitation in acetone, and the amount of maleic anhydride grafted was determined to be 0.08% by weight.

<Manufacture of adhesives>
Polycarbodiimide (manufactured by Nisshinbo Co., Ltd., trade name Carbodilite HMV-8CA) was dry blended with 100 parts by weight of MAH-SEBS produced as described above (parts by weight) shown in Table 1. Then, it was extruded using a twin-screw kneader (manufactured by Nippon Steel Works, TEX-30) at a resin temperature of 250 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 80 g / min to obtain a carbodiimide-modified SEBS adhesive. For the adhesive layer, pellets produced by the above kneader are preheated (220 ° C., 5 minutes), heated press molded (220 ° C., 100 kg / cm ² pressure, 1 minute), cooled press molded (30 And adjusted to a thickness of 100 microns by 50 ° C., 50 kg / cm ² pressure, 5 minutes).

<Laminate resin layer>
For the polar resin (F) layer, a polyethylene terephthalate film (trade name Lumirror manufactured by Toray Industries, Inc.) (100 micron thickness) (hereinafter abbreviated as PET) was used.

The aromatic polymer resin (G) layer is a 300 μm thick acrylonitrile butadiene styrene copolymer (hereinafter abbreviated as ABS) having a melt flow rate of 35.0 and a density of 1.05 g / cm ^3. used.

<Manufacture of laminates>
As shown in Table 1, an ABS film is used as an aromatic polymer resin (G) layer (300 μ), an adhesive film (100 μ) is stacked on top, and PET is further stacked on top of each other, followed by press bonding. It was created. The laminate is made by laminating each film in the order of ABS / adhesive / PET, and pressing and fusing a 60 cm wide hot plate (240 ° C.) from the PET side at a pressure of 50 kg / cm ² for 2 minutes. is there.

<Adhesive strength evaluation of laminate>
The laminate produced above was cut into a width of 15 mm, and the interface between the polar resin (F) layer and the adhesive layer was pulled at 180 ° peel using a tensile tester, and the adhesive strength (unit: g / 15 cm) was 23 ° C. at room temperature. Measured with
These results are shown in Table 1.

  In Example 1, it has a peel strength of 22 N / 15 mm with respect to the polyester layer, and exhibits good adhesiveness.

(Example 2)
<Production of aromatic polymer (A) having a group that reacts with carbodiimide group>
The powder was changed from SEBS-1 in Example 1 to SEBS-2 powder. Next, in the same manner as in Example 1, maleic acid modification was carried out, and the obtained M-SEBS was dissolved in xylene and purified by reprecipitation in acetone. The grafting amount of maleic anhydride was measured and found to be 0.12% by weight. It was.

  The adhesive (D) was manufactured in the same manner as in Example 1 except that the formulation of Example 1 was changed as shown in Table 1, and a laminate was formed.

  The obtained adhesive (D) has a peel strength of 32 N / 15 mm with respect to the polyester layer and exhibits good adhesiveness.

(Example 3)
In the production of the laminate, the adhesive (D) was produced in the same manner as in Example 2 except that ABS was changed to high-density polyethylene, and the laminate was molded.

The polyolefin resin (H) layer, a high density polyethylene (manufactured by Mitsui Chemicals, Inc.) (hereinafter, HDPE for short) has a melt flow rate of 12.0, density of film thickness 100μ is 0.961 g / cm ³ 3 Used in layers.

  The obtained adhesive (D) has a peel strength of 26 N / 15 mm with respect to the polyester layer and exhibits good adhesion.

(Examples 4 to 5)
The adhesive (D) was manufactured in the same manner as in Example 1 except that the formulation of Example 1 was changed as shown in Table 1, and a laminate was formed.

  The obtained adhesive (D) uses an imine-modified resin as a raw material, but exhibits good adhesiveness in the same manner as the carboxylic acid-modified maleic acid-modified resin.

(Comparative Examples 1-2)
When the maleic acid modified resin which is the raw material of the adhesive used in Examples 1 to 2 is used without being modified with carbodiimide, the adhesiveness is inferior.

(Comparative Example 3)
When Mn / (100 * f / M) of the maleic acid-modified resin is greater than 7.5 and 6, a large amount of maleic acid is added to the resin chain. When the amount of polycarbodiimide was large without dilution of the resin, carbodiimide modification could not be performed with a biaxial kneader, and an adhesive could not be produced.

(Comparative Example 4)
When the imine-modified resin that is the raw material of the adhesive used in Examples 3 to 5 is used without being modified with carbodiimide, the adhesiveness is inferior.

(Comparative Example 5)
When the amount of polycarbodiimide is large without dilution of the resin with respect to the imine-modified resin that is the raw material of the adhesive used in Example 3 to Example 5, carbodiimide modification cannot be performed with a biaxial kneader, and the adhesive Could not be manufactured.

  According to the present invention, the carbodiimide chain and the aromatic polymer chain are on the same chain by reacting the aromatic polymer (A) having a group that reacts with the carbodiimide group and the carbodiimide group-containing compound (B). Thus, the adhesive (D) can be efficiently produced, and the adhesive strength of the obtained adhesive is improved.

  It is also possible to select a production method including the unmodified polymer (C) that is difficult to crosslink during production.

  Therefore, by using the adhesive, it is possible to obtain a laminate having excellent interlayer adhesive strength of the polar resin (F), the aromatic polymer (G) and / or the polyolefin (H).

The use of the laminate of the present invention is not particularly limited, but is used for applications that require adhesion between a polar resin and an aromatic polymer, for example, food cups such as jelly cups that are styrene-based molded products, and beverage cups. Is possible.

Claims (6)

An adhesive (D) obtained by reacting an aromatic polymer (A) having a group that reacts with a carbodiimide group and a carbodiimide group-containing compound (B). An adhesive (D) obtained by reacting an aromatic polymer (A) having a group that reacts with a carbodiimide group and a carbodiimide group-containing compound (B) in the presence of an unmodified polymer (C). The adhesive (D) according to claim 1 or 2, wherein the aromatic polymer (A) having a group that reacts with a carbodiimide group is a polymer that satisfies the following formula (1).
0.1 <Mn / (100 * f / M) <6 (1)
(Where
f: Formula weight of a compound having a group that reacts with a carbodiimide group (g / mol)
M: content (% by weight) of a compound residue having a group that reacts with a carbodiimide group
Mn: Number average molecular weight of the polymer (A). ) The adhesive (D) according to claim 1 or 2, wherein the aromatic polymer (A) having a group that reacts with a carbodiimide group is an aromatic polymer and / or an imine-modified aromatic polymer having a maleic acid group. . Furthermore, the adhesive (D) of Claims 1 thru | or 4 containing the substance (E) which provides at least 1 sort (s) of tackiness chosen from a rosin derivative, a terpene resin, a petroleum resin, and those hydrides.   Polar resin (F) and aromatic polymer (G) and / or polyolefin (H) through adhesive (D), or two or more types of polar resin (F) through adhesive (D) A multi-layer laminate formed by bonding.