JP5796310B2 - Modified alicyclic polyester and molded body - Google Patents

Description

The present invention relates to a modified alicyclic polyester and a molded article containing the modified alicyclic polyester. More specifically, the present invention relates to a modified alicyclic polyester having good adhesion to various resins and glass, a molded product thereof, and a laminate having a layer containing the modified alicyclic polyester.
The present invention also relates to a modified alicyclic polyester that can be suitably used as a modifier for polyester resins and polycarbonate resins.

  Polyamide resins and ethylene-vinyl alcohol copolymers are excellent in toughness, heat resistance, wear resistance, and gas barrier properties, and thus have been widely used in industrial products, household products, packaging materials, and the like. Examples of applications utilizing this gas barrier property include beverage bottles and the food packaging field. Specifically, a polyester resin gas barrier property is obtained by laminating a polyamide resin layer or an ethylene-vinyl alcohol copolymer layer on a polyester resin layer such as polyethylene terephthalate having excellent heat resistance, chemical resistance and mechanical properties. Application to a container for carbonated drinks with improved food and packaging materials that enable long-term storage of fresh foods and the like are being studied.

In the lamination of such a polyester resin layer, a polyamide resin layer, and an ethylene-vinyl alcohol copolymer layer, both layers are not heat-sealed, and thus are combined through an adhesive or an adhesive resin. However, there has been a problem that the adhesive strength is lowered during high temperature treatment such as a sterilization treatment process or retort cooking in food packaging applications, and is easily peeled off.
Moreover, in order to give not only gas barrier properties but also impact resistance, flexibility, soft touch, waterproofness, etc., an elastic body may be laminated on a polyamide resin layer or an ethylene-vinyl alcohol copolymer layer. is there. Conventionally, even when an elastic body is laminated on a polyamide resin or an ethylene-vinyl alcohol copolymer, there has been a problem that the heat-fusibility between the two resins is poor and the transparency is also deteriorated. For this reason, conventionally, a laminate having not only gas barrier properties but also flexibility, waterproofness, impact resistance, etc. and excellent transparency has not been obtained.

  As an adhesive for a laminate of a polyester resin layer and a polyamide resin layer or an ethylene-vinyl alcohol copolymer layer, a modified polyester thermoplastic elastomer obtained by modifying with an unsaturated carboxylic acid or a derivative thereof is disclosed. (Patent Documents 1 and 2). However, the laminated body disclosed here is not sufficient in maintaining adhesive strength and transparency after high-temperature treatment.

On the other hand, as one of methods for improving the physical strength, elastic modulus, heat distortion temperature, and the like of a resin, a glass fiber reinforced resin in which a glass fiber is contained as a filler in the resin is generally used. However, if the adhesiveness between the resin and the glass fiber is not sufficient, the physical strength, elastic modulus, heat distortion temperature and the like of the glass fiber reinforced resin are not sufficiently improved.
In addition, a laminate in which resin and glass are laminated (hereinafter sometimes referred to as a glass laminate) is used for anti-scattering glass, insulators, etc., taking advantage of properties such as transparency, insulation, and impact resistance. Widely used. Furthermore, in order to compensate for the shortcomings such as brittleness and large specific gravity of glass, a glass laminate coated with a resin may be used. As described above, since the alicyclic polyester has good transparency and heat resistance, and the glass itself is the same, the glass laminate using the alicyclic polyester does not impair the characteristics of the glass, but has the disadvantages of glass. Is expected to compensate. However, when the alicyclic polyester layer and the glass are laminated, the adhesiveness between the two is insufficient, and thus there is a problem that peeling occurs between the layers.

As a method for solving these problems, the glass surface has been conventionally treated by silane coupling or the like (see Patent Documents 3 and 4). However, the silane coupling treatment on the glass surface may complicate the manufacturing process and may not exhibit a sufficient improvement effect.
As described above, conventionally, molded articles containing an alicyclic polyester layer, that is, resin laminates, glass fiber reinforced resins, glass laminates, and the like have not been able to exhibit their original performance.

JP 2002-155135 A JP 2002-144486 A JP 2006-51608 A International Publication No. 09/044884 Pamphlet

This invention is made | formed in view of this background art, The subject is the modified alicyclic polyester which has transparency and heat resistance, and favorable adhesiveness with various resin and glass, and this modified fat The object is to provide a molded article containing a cyclic polyester.
Furthermore, the present invention provides a modified alicyclic polyester having the above-mentioned performance and further having good impact resistance, flexibility, soft tactile sensation and waterproofness, and a molded article containing the modified alicyclic polyester. Is an issue.

  As a result of intensive studies in view of the above problems, the present inventors have found that the above problems can be solved by using a modified alicyclic polyester in which a specific modification is imparted to the alicyclic polyester. It came to complete.

That is, the gist of the present invention is the following [1] to [ 7 ].
[1] is composed of units and units derived from a diol derived from dicarboxylic acids, modified fat obtained by 0.01-40% by weight grayed raft the vinyl monomers in the cycloaliphatic polyester has a melting point of 160 ° C. or higher 240 ° C. or less a cyclic polyester, alicyclic polyester Le, the proportion of 1,4-cyclohexanedicarboxylic acid in a unit derived from a total dicarboxylic acid 50 mol% or more, 1,4-cyclohexane in the units derived from the total diol proportion of dimethanol of not less than 50 mol%, and the vinyl monomer is an unsaturated carboxylic acid or its derivatives and modified cycloaliphatic polyester, characterized in der Rukoto least one selected from unsaturated silane compounds.

[2] Oite to [1], cycloaliphatic polyester has a hard segment and a soft segment, modified cycloaliphatic polyester comprising polyalkylene ether polyol 3-30% by weight as a soft segment.
[3] [1] or Oite in [2], grafting, modified cycloaliphatic polyesters, characterized in that made by melt-kneading in the presence of an organic peroxide.

[ 4 ] A molded article containing the modified alicyclic polyester according to any one of [1] to [ 3 ].
[ 5 ] A laminate having a layer containing the modified alicyclic polyester according to any one of [1] to [ 3 ] and another layer.
[ 6 ] The laminate according to [ 5 ], wherein the other layer is at least one of a resin layer, a glass layer, and a metal layer.
[7] In [6], laminate a layer consisting of the denaturation cycloaliphatic polyester and the other layers are in contact.

According to the present invention, a modified alicyclic polyester having transparency and heat resistance, and having good adhesion to various resins such as polyamide resin and ethylene-vinyl alcohol copolymer, glass containing glass fiber, and the like It is possible to provide a molded article and a laminate including a layer made of the modified alicyclic polyester.
Furthermore, according to the present invention, there are provided a modified alicyclic polyester having the above-mentioned performance, and further having good impact resistance, flexibility, soft tactile sensation and waterproofness, and a molded article containing the modified alicyclic polyester. can do.

Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and can be arbitrarily modified and implemented without departing from the gist of the present invention.
The modified alicyclic polyester of the present invention is obtained by grafting a vinyl monomer onto an alicyclic polyester.
Here, “grafting” is not used as a copolymer component of the alicyclic polyester in advance, but is a method in which a vinyl monomer is bonded to the alicyclic polyester already produced by reaction. That is, in the present invention, “grafting” means not only when the vinyl monomer is polymerized and introduced as a side chain having a long molecular chain length, but also when the vinyl monomer is chemically bonded to the alicyclic polyester. Is included.
The reason why grafting is more suitable than copolymerization is not clear, but compared to the case where the structural unit corresponding to vinyl monomer is copolymerized with alicyclic polyester, the vinyl monomer is bonded by grafting. However, the molecular movement of the portion corresponding to the vinyl monomer is easy, which is considered to be effective in improving the adhesion to other substances. In other words, the molecular motion of the alicyclic polyester main chain is restrained by the entanglement of the main chains, but the molecular motion of the grafted portion is free without being constrained by the entanglement of the main chains.

<Alicyclic polyester>
The alicyclic polyester used as a raw material for the modified alicyclic polyester of the present invention is not limited as long as it has an alicyclic compound as a raw material monomer, but is preferably a polyester having an alicyclic compound as a main component. . Here, “having an alicyclic compound as a main component” means a polyester containing 50% by weight or more of an alicyclic compound as a repeating unit of the polyester (in other words, as a raw material monomer).
The content of the alicyclic compound constituting the alicyclic polyester is preferably 60% by weight or more, more preferably 70% by weight or more, and further preferably 80% by weight or more. When the content rate of the alicyclic compound which comprises alicyclic polyester is less than the said lower limit, it exists in the tendency for transparency and heat resistance of modified alicyclic polyester to fall. In addition, the upper limit of the content rate of the alicyclic compound which comprises this alicyclic polyester is 100 weight%.
Here, as described later, when the alicyclic polyester in the present invention contains a polyalkylene ether polyol as a soft segment, when calculating the content of the alicyclic compound constituting the alicyclic polyester, The weight of the alkylene ether polyol is excluded and handled.

The alicyclic compound constituting the alicyclic polyester in the present invention may be any of dicarboxylic acid, diol, oxycarboxylic acid, and caprolactone as a raw material monomer, and further, as a compound other than an ester-forming monomer. An alicyclic compound may be used. Preferably, an alicyclic compound is used as any one of dicarboxylic acid, diol, and oxycarboxylic acid, and further, an alicyclic compound is used as at least one of dicarboxylic acid and diol. It is.

When alicyclic dicarboxylic acid is used as a raw material monomer constituting alicyclic polyester, the compound is not limited. For example, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid Cyclohexanedicarboxylic acids such as acids; decahydro such as 1,4-decahydronaphthalenedicarboxylic acid, 1,5-decahydronaphthalenedicarboxylic acid, 2,6-decahydronaphthalenedicarboxylic acid, 2,7-decahydronaphthalenedicarboxylic acid And naphthalenedicarboxylic acids. Of these, cyclohexanedicarboxylic acid is preferred, and 1,4-cyclohexanedicarboxylic acid is particularly preferred.
Two or more of these alicyclic dicarboxylic acids can be used in combination.

When the alicyclic diol is used as a raw material monomer constituting the alicyclic polyester, the compound is not limited. For example, cyclopentane diol such as 1,2-cyclopentanediol and 1,3-cyclopentanediol; 5-membered ring diols such as 2-cyclopentanedimethanol, 1,3-cyclopentanedimethanol, cyclopentanedimethanol bis (hydroxymethyl) tricyclodecane; 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1 Cyclohexanediol such as 1,4-cyclohexanediol; cyclohexanedimethanol such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol; 2,2-bis- (4-hydroxycyclohexyl) ) Biscyclohexyl diol such as bread and the like. Of these, cyclohexanedimethanol is preferred, and 1,4-cyclohexanedimethanol is particularly preferred. Two or more of these alicyclic diols can be used in combination.
These alicyclic dicarboxylic acids and alicyclic diols may be ester-forming derivatives as raw material monomers.

  When the alicyclic compound constituting the alicyclic polyester is a 6-membered ring, the 6-membered ring compound may be a trans isomer or a cis isomer, or a mixture thereof. In order to improve the heat resistance and moldability of the resulting modified alicyclic polyester, it is preferable that the ratio of the trans isomer is high. Specifically, in any of the alicyclic dicarboxylic acid and the alicyclic diol, the trans isomer content is preferably 50 mol% or more, more than 60 mol%, based on the total amount of the trans isomer and the cis isomer. It is more preferable that it is 70 mol% or more. The upper limit of the trans isomer content is usually 100 mol%.

In the alicyclic polyester used in the present invention, a compound other than the alicyclic compound can be used in combination as a raw material monomer. The compound that can be used as the raw material monomer of the alicyclic polyester is not limited, and various dicarboxylic acids, diols, oxycarboxylic acids, caprolactones, polyfunctional compounds, and the like can be used.
Examples of the dicarboxylic acid other than the alicyclic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, phenylenedioxydicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and 4,4 ′. -Aromatic dicarboxylic acids such as diphenyl ether dicarboxylic acid, 4,4'-diphenyl ketone dicarboxylic acid, 4,4'-diphenoxyethane dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid; succinic acid, glutaric acid, adipic acid , Pimelic acid, suberic acid, azelaic acid, sebacic acid, undecadicarboxylic acid, aliphatic dicarboxylic acid such as dodecadicarboxylic acid, and the like. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable, Particularly preferred is terephthalic acid. Two or more dicarboxylic acids other than these alicyclic dicarboxylic acids can be used in combination.

As diols other than the alicyclic diol, in addition to the polyalkylene ether polyol described later, for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, Aliphatic diols such as decamethylene glycol, neopentyl glycol, diethylene glycol; xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4′-hydroxyphenyl) propane, 2,2-bis (4′-) and aromatic diols such as β-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, and bis (4-β-hydroxyethoxyphenyl) sulfonic acid. Among these, 1,4-butanediol and ethylene glycol are preferable in addition to the polyalkylene ether polyol described later, and 1,4-butanediol is particularly preferable. Two or more diols other than these alicyclic diols can be used in combination.
Examples of the polyfunctional compound include triols such as trimellitic acid, pyromellitic acid, and pentaerythritol, tricarboxylic acids, and tetracarboxylic acids.
The raw material monomers other than these alicyclic compounds may also be ester-forming derivatives.

Among the above, as the alicyclic polyester used as a raw material of the modified alicyclic polyester of the present invention, in all dicarboxylic acid units, units derived from 1,4-cyclohexanedicarboxylic acid are preferably 50 mol% or more, more preferably. Is preferably 60 mol% or more, more preferably 70 mol% or more, and particularly preferably 80 mol%. The higher the proportion of units derived from 1,4-cyclohexanedicarboxylic acid in all dicarboxylic acid units, the better the heat resistance of the modified alicyclic polyester, which is preferable. In addition, the upper limit of the ratio of the unit derived from 1, 4- cyclohexanedicarboxylic acid in all dicarboxylic acid units is usually 100 mol%.
As the alicyclic polyester, 1,4-cyclohexanedimethanol is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 70 mol in all diols except for the polyalkylene ether polyol described later. % Or more, particularly preferably 80 mol%. In addition, the upper limit of the ratio of the unit derived from 1,4-cyclohexanedimethanol in all diol units is usually 100 mol%.
In addition, as the alicyclic polyester, structures derived from 1,4-cyclohexanedicarboxylic acid and 1,4-cyclohexanedimethanol are each 50 mol% or more, preferably 60 wt% or more, more preferably on the same basis as above. Is preferably 70% by weight or more from the viewpoint of transparency and heat resistance.

The alicyclic polyester used as a raw material for the modified alicyclic polyester of the present invention may be a so-called block copolymer having a hard segment and a soft segment and containing a polyalkylene ether polyol as the soft segment. Here, the structure of the alicyclic polyester described above corresponds to the hard segment. It is preferable that the alicyclic polyester contains a polyalkylene ether polyol as a soft segment because the flexibility of the modified alicyclic polyester tends to be improved and the adhesion and tackiness tend to be good. The polyalkylene ether polyol is an embodiment of “diol other than alicyclic diol” as described above.
Thus, by including a polyalkylene ether polyol as a soft segment, the modified alicyclic polyester of the present invention can further improve impact resistance, flexibility, soft touch, waterproofness, and the like.

The polyalkylene ether polyol constituting the soft segment is not limited, but among them, polyalkylene ether glycol is preferable. Examples of the polyalkylene ether glycol include polyethylene ether glycol, polypropylene ether glycol, polytrimethylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, and the like. Particularly preferred is polytetramethylene ether glycol. These polyalkylene ether glycols may be used in combination.

  As a raw material of the modified alicyclic polyester of the present invention, when using a block copolymer having a hard segment and a soft segment, in particular, as a hard segment, 1,4-cyclohexanedicarboxylic acid and 1,4-cyclohexanedimethanol A structure containing 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more of the structure derived from it and using polytetramethylene ether glycol as the soft segment is suitable.

  The number average molecular weight of the soft segment, that is, the number average molecular weight of the polyalkylene ether polyol is usually 200 to 4,000, preferably 300 to 3,000, more preferably 500 to 2,500. When the number average molecular weight of the polyalkylene ether polyol is less than the lower limit, sufficient adhesion may not be exhibited. On the other hand, if the number average molecular weight exceeds the upper limit, phase separation in the alicyclic polyester is likely to occur, and the transparency and heat resistance of the resulting modified alicyclic polyester may be lowered. The “number average molecular weight” here is measured by gel permeation chromatography (GPC). For calibration of GPC, a POLYTETRAHYDROFURAN calibration kit manufactured by POLYMERLABORATORIES, UK may be used.

Moreover, although content of the polyalkylene ether polyol in alicyclic polyester is not limited, Usually, 3 to 30 weight%, Preferably it is 6 to 25 weight%. When the content of the polyalkylene ether polyol, which is a soft segment, is less than the above lower limit value, improvement in flexibility, adhesiveness, and tackiness may be insufficient.
On the other hand, when the content of the soft segment exceeds the above upper limit, the transparency and heat resistance of the resulting modified alicyclic polyester may be lowered. In addition, content of the structural unit derived from a polyalkylene ether polyol can be calculated from the preparation ratio at the time of manufacture, or can be quantified by an instrumental analysis method such as ¹ H-NMR spectrum analysis.

The alicyclic polyester used as a raw material for the modified alicyclic polyester of the present invention has a melt flow rate measured at 230 ° C. and a load of 2.16 kg (kgf) in accordance with test condition 4 of JIS K7210. / 10 minutes), preferably 3 to 80 (g / 10 minutes), more preferably 5 to 60 (g / 10 minutes). When MFR exceeds the above upper limit, the heat resistance of the modified alicyclic polyester tends to decrease. If the MFR is less than the lower limit, fluidity may be insufficient, and grafting described later may be difficult.
The intrinsic viscosity (IV) of the alicyclic polyester used in the present invention is preferably 0.5 dl / g or more from the viewpoint of the mechanical strength of the modified alicyclic polyester. On the other hand, from the viewpoint of moldability, it is preferably 1.5 dl / g or less. Here, IV is measured by measuring at 30 ° C. using a Ubbelohde viscometer with a phenol / tetrachloroethane (weight ratio 1/1) mixture as a solvent.

  The melting point of the alicyclic polyester used as a raw material for the modified alicyclic polyester of the present invention is not limited, but is usually 160 ° C. or higher, preferably 180 ° C. or higher, more preferably 200 ° C. from the viewpoint of the balance between processability and transparency. It is above, and is 240 degrees C or less normally, Preferably it is 230 degrees C or less. The melting point of the alicyclic polyester was raised from room temperature to 250 ° C. at a temperature rising rate of 100 ° C./min using a differential scanning calorimeter (DSC) and held for 3 minutes, and then cooled to −100 ° C. It is the temperature of the melting peak when the temperature is raised to 250 ° C. at a rate of temperature increase of 10 ° C./min after cooling at 10 ° C./min.

<Vinyl monomer>
In the present invention, the vinyl monomer grafted to the alicyclic polyester is not limited as long as it has a double bond in the molecule, and may be a polar compound or a nonpolar compound. .

Specific examples of polar vinyl monomers typically include unsaturated carboxylic acids or derivatives thereof, and ethylenically unsaturated silane compounds.
Examples of the unsaturated carboxylic acid or derivative thereof include (meth) acrylic acid, ethacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid. Illustrated. Further, derivatives of these acids, specifically, acid anhydrides, esters, acid halides, amides, imides and the like may be used, and acid anhydrides are particularly preferable. Of these, maleic acid or its anhydride is particularly preferred. Here, “(meth) acrylic acid” means acrylic acid or methacrylic acid, and the same applies hereinafter.

Specifically, the unsaturated silane compound is preferably an ethylenically unsaturated silane compound represented by the following general formula (I).
R1 · SiR2 _n Y _3-n (I)
In formula (I), R1 represents an ethylenically unsaturated hydrocarbon group or hydrocarbonoxy group, R2 represents a hydrocarbon group, Y represents a hydrolyzable organic group, and n is an integer of 0-2.
Here, as R1, preferably an ethylenically unsaturated hydrocarbon group or a hydrocarbonoxy group having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, specifically, a vinyl group, a propenyl group, Examples include butenyl group, cyclohexenyl group, and γ- (meth) acryloyloxypropyl group.

R2 is preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, n -Alkyl or alkenyl groups represented by butyl group, i-butyl group, decyl group, phenyl group, cyclohexyl group, etc .; alkoxy such as hydroxyethyl group, β-methoxyethyl group, γ- (meth) acryloxypropyl group Alkyl group; oxygen-containing and / or nitrogen-containing hydrocarbon group such as β-aminoethyl group, γ-aminopropyl group, γ-glycidoxypropyl group; chloromethyl group, β-chloroethyl group, γ-chloropropyl group, etc. And the like.
Y is preferably a hydrolyzable organic group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, specifically, a methoxy group, an ethoxy group, an isopropoxy group, or a β-methoxyethoxy group. , Formyloxy group, acetoxy group, propionyloxy group, alkylamino group, arylamino group and the like, among which alkoxy group is desirable.

  Specific examples of such unsaturated silane compounds include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-methacryloyloxypropyltrimethoxysilane, etc. Among these, odor etc. From the viewpoint, vinyltrimethoxysilane is preferably used.

Specific examples of vinyl monomers having polarity other than unsaturated carboxylic acid or derivatives thereof and ethylenically unsaturated silane compounds include, for example, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxy Hydroxy (meth) acrylates such as propyl (meth) acrylate; unsaturated glycidyl group-containing compounds such as glycidyl (meth) acrylate and monoglycidyl itaconate; aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate , (Meth) acrylic acid aminoalkyl ester derivatives such as dimethylaminoethyl (meth) acrylate and aminopropyl (meth) acrylate; allylamine derivatives such as allylamine, methacrylamine and N, N-dimethylacrylamide And the like.

  Specific examples of nonpolar vinyl monomers include, for example, styrene such as styrene, methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorostyrene, and derivatives thereof; methyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as ethyl, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; (meth) acrylic acid And esters of 1 to 20 carbon atoms; (meth) acrylonitrile, vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl triol acetate, etc. The body etc. can be mentioned. Of these, styrene and methyl methacrylate are preferred.

The above vinyl monomers may be used alone or in combination of two or more.
In the present invention, as the vinyl monomer to be grafted to the alicyclic polyester, among the above vinyl monomers, it is particularly preferable to use a vinyl monomer having polarity. By using a vinyl monomer having polarity, the adhesiveness of the modified alicyclic polyester of the present invention tends to be good. Of these, unsaturated carboxylic acids or derivatives thereof, and ethylenically unsaturated silane compounds are preferred.

<Grafting>
The modified alicyclic polyester of the present invention is obtained by grafting the above alicyclic polyester with the above vinyl monomer. Any method may be used for grafting to obtain a modified alicyclic polyester, which may be a reaction only with heat, irradiation with an electron beam or ionizing radiation, etc., but an organic peroxidation that generates radicals during the reaction. A product or the like may be added as a radical generator and reacted. Examples of the reaction method include a solution modification method in which a reaction is performed in a solvent, a melt modification method without using a solvent, and the like, and other methods such as an aqueous suspension polymerization method may be used. Of these methods, grafting is preferably performed by melt kneading in the presence of an organic peroxide, which is one form of the melt modification method described later. Advantages of adopting this method include that a continuous production is possible and no solvent remains in the resulting modified alicyclic polyester because no solvent is used.

  Examples of the melt modification method include a method in which an alicyclic polyester, a vinyl monomer, and a radical generator, which will be described later, are mixed in advance and then melt-kneaded and reacted in a kneader, or an alicyclic polyester melted in a kneader. In addition, a method in which a mixture of a radical generator dissolved in a solvent or the like and a vinyl monomer is added from the inlet and allowed to react can be used. Usually, a Henschel mixer, a ribbon blender, a V-type blender or the like is used for mixing, and a single or twin screw extruder, a roll, a Banbury mixer, a kneader, a Brabender mixer, or the like can be used for melt kneading. As the melt-kneading conditions, for example, in a single-screw or twin-screw extruder, extrusion is preferably performed at a temperature of about 150 to 300 ° C.

  The blending ratio of the alicyclic polyester and the vinyl monomer is not limited, but the vinyl monomer is usually 0.01 to 30 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 100 parts by weight of the alicyclic polyester. Is preferably blended at a ratio of 0.1 to 5 parts by weight. If the amount of vinyl monomer is too small relative to the alicyclic polyester, the predetermined amount of modification necessary for achieving the effects of the present invention may not be obtained. If the amount of vinyl monomer is too large, a large amount of unreacted vinyl monomer may be obtained. And may adversely affect adhesiveness.

Specific examples of the radical generator include, but are not limited to, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne -3, lauroyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert Organic peroxides and organic peresters such as butyl perbenzoate, tert-butyl perisobutylate, tert-butyl perpivalate, and cumyl perpivalate, azobisisobutyronitrile, dimethylazoisobutyrate An azo compound such as a rate can be used.

These radical generators can be appropriately selected according to the type of alicyclic polyester, the type of vinyl monomer, and the reaction conditions, and two or more types may be used in combination.
The amount of the radical generator is usually 0.001 to 20 parts by weight, preferably 0.005 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, particularly preferably 100 parts by weight of the alicyclic polyester. Is 0.01 to 3 parts by weight. If the amount of the radical generator is too small relative to the vinyl monomer, the predetermined amount of modification necessary for achieving the effects of the present invention cannot be obtained, and if too large, the moldability of the modified alicyclic polyester is greatly increased. There is a possibility of getting worse.

As the solution modification method, a method can be used in which alicyclic polyester is dissolved in an organic solvent and the like, and a radical generator and a vinyl monomer are added thereto for grafting. The organic solvent is not particularly limited, and for example, alkyl group-substituted aromatic hydrocarbons and halogenated hydrocarbons can be used.
As an aqueous suspension polymerization method, first, an emulsifier is dissolved in water, an alicyclic polyester is dispersed therein, a vinyl monomer is added thereto, the temperature is increased, and the alicyclic polyester is impregnated with the vinyl monomer. . Two or more types of radical polymerization initiators having different decomposition temperatures are added to this aqueous suspension, and after heating to a temperature at which only one radical polymerization initiator is substantially decomposed, a grafting precursor is obtained. The modified alicyclic polyester of the present invention can be obtained by melt-kneading the grafted precursor at a temperature at which the radical polymerization initiator having a high decomposition temperature decomposes.

<Modified alicyclic polyester>
The modified alicyclic polyester of the present invention has a graft amount of vinyl monomer in the modified alicyclic polyester of 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 0.5% by weight or more. Yes, it is 40% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less. When the graft amount of the vinyl monomer is less than the lower limit value, the number of functional groups is small and the effect becomes poor. On the other hand, when the graft amount of the vinyl monomer exceeds the upper limit, the remaining unreacted monomer increases, which is not preferable.
In addition, the graft amount of the vinyl monomer in the modified alicyclic polyester can be confirmed by a known method, and the ICI emission analysis method using ¹ H-NMR, infrared absorption spectrum, and high-frequency plasma emission analyzer. Etc. can be confirmed.

Specifically, when an unsaturated carboxylic acid or derivative thereof is used as the vinyl monomer, the graft amount is measured by press-molding a modified alicyclic polyester into a sheet having a thickness of 100 μm as a test sample, and an infrared absorption spectrum. This can be determined by measuring the absorption specific to the carboxylic acid or its derivative in the resin (the carbonyl characteristic absorption of 1900 to 1600 cm ⁻¹ (C═O stretching vibration band)).
When using an ethylenically unsaturated silane compound as the vinyl monomer, the amount of grafting is measured by burning the sample by heating and ashing. It can be confirmed by ICI emission spectrometry using an analyzer.
In the grafting of the vinyl monomer, 100% of the vinyl monomer is not subjected to the graft reaction, and the vinyl monomer that has not reacted with the alicyclic polyester may remain. In the present invention, the graft amount means a value obtained by directly measuring the alicyclic polyester by the method as described above, and may include an unreacted vinyl monomer.

The melting point of the modified alicyclic polyester of the present invention is not limited, but is usually 160 ° C. or higher, preferably 180 ° C. or higher, more preferably 200 ° C. or higher, and usually 240 ° C. or lower, in terms of the balance between processability and transparency. Preferably, it is 230 degrees C or less. In addition, the measuring method of melting | fusing point of modified alicyclic polyester is the same as the measuring method of melting | fusing point of alicyclic polyester used as a raw material as above-mentioned.
The modified alicyclic polyester of the present invention has a melt flow rate measured at 230 ° C. under a load of 2.16 kg (kgf) in accordance with JIS K7210 test condition 4, usually 1 to 100 (g / 10 min), preferably 3 Those having a range of ˜80 (g / 10 minutes), more preferably 5 to 60 (g / 10 minutes) are suitable. When MFR exceeds the above upper limit, the heat resistance of the modified alicyclic polyester tends to decrease. If MFR is less than the above lower limit, the fluidity is insufficient and the moldability tends to deteriorate.

<Composition>
The modified alicyclic polyester of the present invention may be a composition containing components other than the modified alicyclic polyester as long as the object or effect of the present invention is not significantly impaired. Examples of such components include resins other than modified alicyclic polyesters, elastomers, and various additives.
Examples of resins other than modified alicyclic polyesters include polyolefin resins such as polyethylene; polyester resins such as polybutylene terephthalate and polyethylene terephthalate; polyamide resins; polycarbonate resins; polystyrene resins, polyphenylene ethers; Examples include oxymethylene; polyphenylene sulfide; acrylic resin, petroleum resin, acrylonitrile-butadiene-styrene copolymer, and polyvinyl chloride resin.

Various additives include lubricants, antiblocking agents, antioxidants, heat stabilizers, UV absorbers, light stabilizers, antistatic agents, colorants, flame retardants, metal powders, dispersants, coupling agents, and neutralization. Agents, foaming agents, cross-linking agents, crystal nucleating agents, rust inhibitors, inorganic and / or organic fillers, and the like.
Examples of the lubricant include bisamide compounds. Examples of the antioxidant include hindered phenol compounds. Examples of the flame retardant include inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide; halogen-based and phosphorus-based organic flame retardants, and the like.

<Polycarbonate resin composition>
The modified alicyclic polyester of the present invention is characterized by excellent compatibility with a polycarbonate resin. For this reason, the modified alicyclic polyester of the present invention is suitable for use as a compatibilizing agent in a resin composition with a polycarbonate resin or a resin composition with a polycarbonate resin and another resin.

<Molded body>
There is no limitation in the molded object obtained from the modified alicyclic polyester of this invention, It can be set as various extrusion molded products, injection molded products, etc. Moreover, although it can also be set as molded objects, such as an injection molded product and single layer sheet which used the modified | denatured alicyclic polyester of this invention independently, it is more effective when it uses as a laminated body mentioned later.

<Laminate>
Since the modified alicyclic polyester of the present invention is excellent in adhesive strength with various materials, it can be suitably used as a laminate having a layer containing the modified alicyclic polyester of the present invention and other layers. it can. There are no limitations on the material for forming the other layers. In addition to resin laminates laminated with other resins, glass laminates laminated with glass, metals such as aluminum, other inorganic substances, paper, wood, etc. It may be laminated. Furthermore, the laminated body which used these materials together may be sufficient. The modified alicyclic polyester of the present invention can exhibit particularly good adhesiveness when used as a layer in contact with these other layers.

<Resin laminate>
The resin laminate of the present invention is a laminate laminated in two or more layers including the layer containing the above-described modified alicyclic polyester of the present invention. The shape of the resin laminate is not limited, and any shape such as a flat shape such as a film, a sheet, or a plate shape, a pipe shape, a bag shape, or an indefinite shape may be used.
The material of the resin layer laminated together with the layer containing the modified alicyclic polyester (hereinafter sometimes referred to as “other resin layer”) is not limited, but specifically, polyolefin resin, polyamide resin, polyester resin Thermoplastic resins such as styrene resin, acrylic resin, polycarbonate resin, and polyvinyl chloride resin are used. These resins may be a resin composition layer containing a plurality of resins.
In addition, you may use the layer which consists of modified alicyclic polyester in the resin laminated body of this invention as a composition with resin etc. which were illustrated above.

  The polyolefin resin used for the other resin layer is not limited, and specific examples include a C2-C4 α-olefin such as ethylene, propylene, and 1-butene, or a copolymer containing these as one component. It is done. Specifically, these polyolefin resins are not limited to homopolymers such as polyethylene, polypropylene, poly-1-butene, and the like, as long as the main component is an α-olefin having 2 to 4 carbon atoms. It also includes a copolymer with ~ 20 α-olefin or a vinyl compound such as vinyl acetate, vinyl alcohol, vinyl chloride, acrylic acid, methacrylic acid, styrene. Further, it may be modified with an unsaturated carboxylic acid such as maleic anhydride, maleic acid, acrylic acid or a derivative thereof. Further, these polyolefin resins may be a mixture of two or more.

  Among polyolefin resins used for other resin layers, when used for a resin laminate requiring gas barrier properties, ethylene-vinyl alcohol copolymer (EVOH) or saponified ethylene-vinyl acetate copolymer is preferable. Used for. A 100% saponified ethylene-vinyl acetate copolymer is equivalent to an ethylene-vinyl alcohol copolymer. Since the modified alicyclic polyester of the present invention has good adhesion to an ethylene-vinyl alcohol copolymer (EVOH) or an ethylene-vinyl acetate copolymer saponified product, the resin laminate with these is transparent. Thus, a resin laminate having good heat resistance and good gas barrier properties can be obtained.

The polyamide resin used in the other resin layers is not limited, but specifically, aliphatic diamines such as hexamethylene diamine and decamethylene diamine, diamines such as alicyclic diamine and aromatic diamine, and adipic acid and sebacic acid. Polyamides obtained by polycondensation with aliphatic dicarboxylic acids such as cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, and dicarboxylic acids such as aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; aminocarboxylic acids such as ε-aminocaproic acid Examples include polyamides obtained by acid condensation; polyamides obtained from lactams such as ε-caprolactam, and copolymerized polyamides composed of these components. Specifically, nylon 6, nylon 66, nylon 610, nylon 9, nylon 11, nylon 12, nylon 6/66 copolymer, nylon 66/610 copolymer, nylon 6/11 copolymer and the like can be mentioned. Among these, nylon 6 and nylon 66, which are excellent in melting point and rigidity, are preferable.
Since the modified alicyclic polyester of the present invention has good adhesion to the polyamide resin, the resin laminate with the polyamide resin has good transparency and heat resistance, and good gas barrier properties. Can be obtained.

  Various additives can be mix | blended with the resin laminated body of this invention in arbitrary layers. Only one type of additive may be used, or two or more types may be used in any combination and ratio. Examples of additives include heat stabilizers, weathering stabilizers, antiblocking agents, slip agents, antistatic agents, flame retardants, neutralizers for catalyst residues, pigments, dyes, inorganic and / or organic fillers. Such commonly used additives can be blended within a range not impairing the object of the present invention.

As a method for producing the resin laminate of the present invention, conventionally known methods can be appropriately employed. For example, co-extrusion methods such as T-die molding and inflation molding, extrusion laminating and pasting at least one layer in advance and laminating other layers thereon, co-injection molding and the like can be mentioned.
Moreover, after obtaining the laminated body by the above molding, the resin laminated body of the present invention can be made into a stretched laminated body by stretching. The stretched laminate may be heat-set, or may be a product without being heat-set. In the case where heat setting is not performed, the stretched laminate is heated to release stress and shrink, so that it can be used as a shrink film.
Furthermore, these can be made into a draw-formed container or the like through secondary processing such as vacuum forming or pressure forming.

  The thickness of each layer of the resin laminate of the present invention can be arbitrarily set depending on the layer configuration, application, required physical properties, etc., but is usually 1 to 1000 μm, preferably 3 to 200 μm, more preferably 5 to 5 in an unstretched state. It is 100 micrometers, More preferably, it is 10-50 micrometers. Moreover, although the thickness of an extending | stretching laminated body is also arbitrary, it is 0.1-100 micrometers normally, Preferably it is 0.3-30 micrometers, More preferably, it is 0.5-20 micrometers.

  The modified alicyclic polyester of the present invention is excellent in adhesive strength with various resins and has excellent transparency and heat resistance. For this reason, the resin laminate of the present invention does not cause delamination and can maintain the excellent characteristics of the resin constituting each layer. For this reason, gas barrier properties including anti-content shielding properties (flavor properties, fragrance retention properties), design properties (surface glossiness, transparency), mechanical strength, shrinkability, etc. have been improved. Gasoline tanks, edible oil bottles It can be suitably used for general food packaging materials such as livestock packaging films such as meat and ham, medical packaging materials, design packaging and labels.

<Bundling agent for glass fiber>
The modified alicyclic polyester of the present invention has good adhesion to various resins and good adhesion to glass, and therefore can be suitably used as a sizing agent for glass fibers.
The sizing agent for glass fibers using the modified alicyclic polyester of the present invention has a better effect of improving the mechanical properties of various resins using glass fibers than known silane coupling agents. This is because, in the case of a silane coupling agent, the crystallinity of the silane coupling agent is not (or extremely low), whereas the modified alicyclic polyester has crystallinity, and therefore an improvement in cohesion can be expected.

When the modified alicyclic polyester of the present invention is used as a sizing agent for glass fibers, the resin can be used as a solution such as a molten or organic solvent, or as an emulsion in which the modified alicyclic polyester of the present invention is dispersed in water. Also good.
When the modified alicyclic polyester of the present invention is used as a sizing agent for glass fibers, an unsaturated silane compound is preferably used as a vinyl monomer.

The amount of the modified alicyclic polyester as a glass fiber sizing agent with respect to the glass fiber is not limited, but is usually 0.1% by weight or more, preferably 0.3% by weight or more, and usually 3% by weight or less, preferably 2% by weight. % Or less. If the amount of the modified alicyclic polyester is less than the lower limit, the fiber is not sufficiently converged and easily fuzzed, and the adhesion between the fiber and the matrix resin tends to be inferior. On the other hand, the amount of the modified alicyclic polyester If the upper limit is exceeded, the fiber bundles are not sufficiently defibrated when the glass fibers are mixed into the resin, which may cause defects due to the presence of undefibrated fiber bundles in the matrix resin. .
The glass fiber sizing agent can be suitably used for both short fibers and long fibers. The glass fiber processing method is not particularly limited, and any known processing method may be used.

<Application>
The modified alicyclic polyester of the present invention has transparency and heat resistance, and exhibits excellent adhesion to various resins and glass, and therefore can be applied to various applications utilizing these characteristics. Specifically, in addition to the above gasoline tanks, edible oil bottles, general food packaging materials such as livestock packaging films such as ham, medical packaging materials, design packaging, labels, etc., gas containers, gas piping, etc. It can also be used as a part for packing or sealing used in the joint part.
Moreover, the modified alicyclic polyester of the present invention is suitably used as a fiber reinforced plastic (FRP) which is a material for parts of fishing boats, leisure boats, skis, water tanks, automobiles, etc., by using it as a glass fiber sizing agent. can do.

EXAMPLES Hereinafter, although this invention is demonstrated still in detail using an Example, this invention is not limited by a following example, unless the summary is exceeded.
The raw materials used in the following examples and comparative examples are as follows.

(A-1) Alicyclic polyester polymer Polyester obtained by polycondensation of 1,4-cyclohexanedicarboxylic acid and 1,4-cyclohexanedimethanol.
(Transformation rate of 1,4-cyclohexanedicarboxylic acid is 88%. Transformation rate of 1,4-cyclohexanedimethanol is 69%. Melting point measured with a differential scanning calorimeter (DSC) at a heating rate of 10 ° C./min. Is 211 ° C. According to test condition 4 of JIS standard K7210, the melt flow rate measured at 230 ° C. and a 2.16 kg load (kgf) is 50 g / 10 min)

(A-2) Alicyclic polyester block polymer Polyether ester having a copolymer of 1,4-cyclohexanedicarboxylic acid and 1,4-cyclohexanedimethanol as a hard segment and polytetramethylene ether glycol as a soft segment Block copolymer.
(15% by weight of polytetramethylene ether glycol content quantified by ¹ H-NMR. 85% trans ratio of 1,4-cyclohexanedicarboxylic acid. 69% trans ratio of 1,4-cyclohexanedimethanol. Differential scanning heat. Using a measuring device (DSC), the melting point measured at a rate of temperature increase of 10 ° C./min is 202 ° C. According to test condition 4 of JIS standard K7210, the melt flow rate measured at 230 ° C. and 2.16 kg load (kgf) is 35g / 10min.)

(B-1) Unsaturated carboxylic acid anhydride Maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade)
(B-2) Organosilane Vinyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-3100)
(C-1) Radical generator Benzoyl peroxide (NIPPER BMT-K40, manufactured by NOF Corporation)

Example 1
100 parts by weight of the alicyclic polyester polymer (a-1), 2 parts by weight of the unsaturated carboxylic acid anhydride (b-1), and 0.5 parts by weight of the radical generator (c-1) are blended, This was melt kneaded at a temperature of 200 to 240 ° C., a screw rotation speed of 200 rpm, and an extrusion rate of 10 kg / hour using a twin screw extruder PCM30 (Ikegai Iron Works, D = 30 mmφ, L / D = 32), and then a pelletizer. To obtain a modified alicyclic polyester. The graft amount of the obtained modified alicyclic polyester was 2%.

<Thermal fusion test 1>
The obtained resin composition was molded into a film having a thickness of 50 to 100 μm by press molding (temperature 240 ° C., press pressure 100 kgf / m ² , preheating 4 minutes, pressurization 2 minutes, cooling 2 minutes).
Separately, a polyamide 6 resin (manufactured by Mitsubishi Engineering Plastics Co., Ltd., Novamid 1020CA2) is press-molded into a film having a thickness of 50 to 100 μm in the same manner as the resin composition except that the temperature is 260 ° C. did.
The film of the resin composition and the adherend film of polyamide 6 resin were overlapped and heat sealed (temperature 240 ° C., seal pressure 2 kgf / m ² , seal time 5 to 10 seconds) and fused to obtain a laminate.
The obtained laminate is cut into a strip shape having a width of 15 mm, and the resin composition layer and the adherend resin layer are peeled off at 23 ° C. in a 180 ° direction at a pulling speed of 300 mm / min in accordance with JIS K-6854. The peel strength (kgf / 15 mm) of the fused surfaces of both layers was measured <T peel peel test>. The results of the obtained peel strength are shown in Table-1.

<Thermal fusion test 2>
Laminate in the same manner as in the heat fusibility test 1 except that an ethylene-vinyl alcohol copolymer (EVOH) (Kuraray Co., Ltd., Eval EP-F101A) was used as the adherend resin instead of the polyamide 6 resin. Then, the peel strength (kgf / 15 mm) was measured under the same conditions as in the heat fusibility test 1. The results of the obtained peel strength are shown in Table-1.

(Examples 2 and 3)
Example 1 except that the blending ratio of the alicyclic polyester polymer (a-1), the unsaturated carboxylic acid anhydride (b-1), and the radical generator (c-1) was as shown in Table 1. In the same manner, a resin composition was obtained. Using the obtained resin composition, the results of evaluation of thermal fusion measurement 1 and thermal fusion measurement 2 in the same manner as in Example 1 are shown in Table 1.
(Examples 4 and 5)
Replacing the alicyclic polyester polymer (a-1) with an alicyclic polyester block polymer (a-2), an unsaturated carboxylic acid anhydride (b-1) and a radical generator (c-1) A resin composition was obtained in the same manner as in Example 1 except that the blending ratio was as shown in Table-1. Using the obtained resin composition, the results of evaluation of thermal fusion measurement 1 and thermal fusion measurement 2 in the same manner as in Example 1 are shown in Table 1.

(Comparative Examples 1 and 2)
As shown in Table-1, the alicyclic polyester polymer (a-1) or the alicyclic polyester block polymer (a-2) was used as it was instead of the resin composition, and the same as in Example 1. Evaluation of heat fusibility measurement 1 and heat fusibility measurement 2 was performed. The results are shown in Table-1.

(Example 6)
100 parts by weight of the alicyclic polyester polymer (a-1), 2 parts by weight of the organosilane (b-2), and 0.5 parts by weight of the radical generator (c-1) are blended. Using a shaft extruder PCM30 (Ikekai Tekko Co., Ltd., D = 30 mmφ, L / D = 32), melt-kneaded at a temperature of 200 to 240 ° C., a screw speed of 200 rpm, and an extrusion rate of 10 kg / hour, and then pelletized through a pelletizer. Thus, a resin composition was obtained.

<Measurement of heat-fusibility 3>
The obtained resin composition was molded into a sheet having a thickness of 1.5 mm by press molding (temperature 240 ° C., press pressure 100 kgf / m ² , preheating 4 minutes, pressurization 2 minutes, cooling 2 minutes). This was overlapped with a 5 mm thick glass plate (parallel glass) and heat-sealed with a press using a 6 mm thick spacer (temperature 240 ° C., press pressure 50 kgf / m ² , preheating 2 minutes, pressurization) 3 minutes, cooling 3 minutes).
After cutting the resin composition side of the obtained laminate with a width of 15 mm to the depth at which the layer of the resin composition is divided, the resin composition layer for the 15 mm width is 23 ° C. using a tensile tester. The peel strength (unit: kgf / 15 mm) of the fused surface of the adhesive polymer composition / glass plate when peeled at 90 ° peeling method and 10 mm / min was measured.
The case where peeling on the fused surface did not occur and the resin composition layer itself was broken was regarded as “no peeling”, and the results are shown in Table 2.

(Examples 7 and 8)
Except that the blending ratio of the alicyclic polyester polymer (a-1), the organosilane (b-2), and the radical generator (c-1) was as shown in Table 2, it was the same as in Example 6. A resin composition was obtained. Table 2 shows the results of evaluating the heat-fusibility measurement 3 in the same manner as in Example 6 using the obtained resin composition.
(Examples 9 and 10)
The alicyclic polyester polymer (a-1) is replaced with the alicyclic polyester block polymer (a-2), and the blending ratio of the organosilane (b-2) and the radical generator (c-1) is changed. A resin composition was obtained in the same manner as in Example 6 except that it was as shown in Table-2. Table 2 shows the results of evaluating the heat-fusibility measurement 3 in the same manner as in Example 6 using the obtained resin composition.

(Comparative Examples 3 and 4)
As shown in Table 2, using the alicyclic polyester-based polymer (a-1) or the alicyclic polyester-based block polymer (a-2) as it is instead of the resin composition, the same as in Example 6. Thus, evaluation of heat-fusibility measurement 3 was performed. As a result, all of Comparative Examples 3 and 4 were easily peeled, and the peel strength was 0 kgf / 15 mm. The results are shown in Table-2.

Claims (7)

Is composed of units and units derived from a diol derived from dicarboxylic acids, modified cycloaliphatic polyester obtained by 0.01-40% by weight grayed raft the vinyl monomers in the cycloaliphatic polyester has a melting point of 160 ° C. or higher 240 ° C. or less a is, the alicyclic polyester Le is in a unit derived from a total dicarboxylic acid 1,4-cyclohexane ratio of dicarboxylic acid 50 mol% or more, in a unit derived from the entire diol 1,4-cyclohexanedimethanol ratio 50 is a mol% or more, and the vinyl monomer is an unsaturated carboxylic acid or its derivatives and modified cycloaliphatic polyester, characterized in der Rukoto least one selected from unsaturated silane compounds. The modified alicyclic polyester according to claim 1, wherein the alicyclic polyester has a hard segment and a soft segment, and contains 3 to 30% by weight of a polyalkylene ether polyol as the soft segment. The modified alicyclic polyester according to claim 1 or 2, wherein the grafting is performed by melt kneading in the presence of an organic peroxide. The molded object containing the modified alicyclic polyester of any one of Claims 1-3 . The laminated body which has a layer containing the modified alicyclic polyester of any one of Claims 1-3 , and another layer. The laminate according to claim 5 , wherein the other layer is at least one of a resin layer, a glass layer, and a metal layer. The laminate according to claim 6, characterized in that a layer consisting of the denaturation cycloaliphatic polyester and the other layers are in contact.