Carbodiimide compound, graft-modified product, olefinic resin composition, adhesive, and laminate

Abstract

To provide a compound that can be suitably employed in producing a graft-modified product capable of forming a layer exhibiting high adhesion strength to a polar group-containing substrate or layer even within a short time.SOLUTION: Provided is a carbodiimide compound represented by the following formula (1). [In formula (1), R1 is a hydrogen atom or a methyl group, R2 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, which optionally includes a substituent, A is an alkylene group, m is an integer of 2 or more, and n is an integer of 1 or more].SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a carbodiimide compound, a graft-modified product, an olefin resin composition, an adhesive, and a laminate.

Background Art

[0002] Polyolefins are widely used as packaging materials and coating materials such as films, sheets, and bottles, or decorative materials such as wallpapers. Since polyolefins usually do not have polar groups in their molecules, they tend to have poor compatibility with polar resins and poor adhesiveness to metals, glass, paper, or polar resins. For this reason, the use of polyolefins by blending them with these materials or laminating them on these materials is restricted.

[0003] In order to solve such problems, conventionally, a method of grafting a polar group-containing monomer onto a polyolefin to improve the above-described compatibility or adhesiveness has been known. For example, a method of producing a modified polyolefin by grafting glycidyl (meth) acrylate or the like onto a polyolefin is known (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Although the modified polyolefin obtained by the method described in Patent Document 1 and the like has improved adhesiveness to some extent, the adhesive strength may still not be sufficient, or it may take a long time to exhibit sufficient adhesive strength.

[0006] One object of the present disclosure is to provide a graft-modified product capable of forming a layer with high adhesive strength on a substrate or layer having a polar group in a short time. One object of the present disclosure is to provide a compound that can be suitably used for producing such a graft-modified product.

Means for Solving the Problems

[0007] One embodiment of the carbodiimide compound of the present disclosure is represented by formula (1).

Chemical formula

Advantages of the Invention

[0008] According to the present disclosure, it is possible to provide a graft-modified product capable of forming a layer with high adhesive strength on a substrate or layer having a polar group even in a short time (for example, a short sealing time). According to the present disclosure, it is possible to provide a carbodiimide compound that can be suitably used for producing such a graft-modified product.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0010] Hereinafter, embodiments of the present disclosure will be described in detail. Each component described in this specification can be used singly or in combination of two or more thereof. In this specification, the term "polymer" may be used without particularly distinguishing between homopolymers and copolymers. That is, the term "polymer" is used to mean either a homopolymer or a copolymer.

[0011] In this specification, the numerical range n1 to n2 means n1 or more and n2 or less when n1 < n2, and means n2 or more and n1 or less when n1 > n2. In this specification, when a lower limit value and an upper limit value are each described a plurality of times in the description of an element, a numerical range formed by combining a value arbitrarily selected from the described lower limit values and a value arbitrarily selected from the described upper limit values is also regarded as being described.

[0012] [Carbodiimide compound] The carbodiimide compound of the present disclosure is represented by the formula (1). In this specification, the carbodiimide compound represented by the formula (1) is also referred to as "carbodiimide compound (1)".

[0013] [Chemical formula]

[0014] In formula (1), R 1 is a hydrogen atom or a methyl group, and a methyl group is preferable from the viewpoint that a graft-modified product excellent in adhesion strength to a substrate or layer having a polar group can be easily obtained.

[0015] In formula (1), R 2 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. The carbodiimide compound (1) having such an aliphatic hydrocarbon group tends to be excellent in solubility in a solvent and ease of synthesis. The number of carbon atoms of the aliphatic hydrocarbon group is 1 to 20, preferably 3 or more, more preferably 12 or less, still more preferably 8 or less, and particularly preferably 7 or less.

[0016] Examples of the substituent include a halogen atom, an alkoxy group, an amino group, an alkylsilyl group, an alkoxysilyl group, a carbonyl group, an amide group, a sulfide group, a carboxylic acid ester group, a sulfonic acid ester group, and a phosphate ester group. When the substituent has a carbon atom, the number of carbon atoms in the substituent is, for example, 8 or less.

[0017] The aliphatic hydrocarbon group may be linear or may contain an alicyclic ring. The aliphatic hydrocarbon group may be straight-chain or may have a branch. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and a saturated aliphatic hydrocarbon group is preferred.

[0018] As the aliphatic hydrocarbon group, an alkyl group is preferred from the viewpoint of easily obtaining a graft-modified product having excellent adhesion strength to a substrate or layer having a polar group, particularly a substrate or layer containing polyester. Examples of the alkyl group include a linear alkyl group and a branched alkyl group.

[0019] Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an icosyl group.

[0020] Examples of the alkyl group having a branch include an isopropyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a 1-methylbutyl group, a 1,2-dimethylpropyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylpropyl group, a 1,1-dimethylpropyl group, a 2,2-dimethylpropyl group, a 1-methylpentyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 1,2,2-trimethylpropyl group, a 2-methylpentyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 2-ethylbutyl group, a 3-methylpentyl group, a 3,3-dimethylbutyl group, a 4-methylpentyl group, a 1-ethyl-2-methylpropyl group, a 1-ethylbutyl group, a 1,1-dimethylbutyl group, a 1,1,2-trimethylpropyl group, a 1-ethyl-1-methylpropyl group, a 1-methylhexyl group, a 1,2-dimethylpentyl group, a 1,3-dimethylpentyl group, a 1,4-dimethylpentyl group, a 1,2,3-trimethylbutyl group, a 1,2,2-trimethylbutyl group, a 1,3,3-trimethylbutyl group, a 2-methylhexyl group, a 2,3-dimethylpentyl group, a 2,4-dimethylpentyl group, a 2,3,3-trimethylbutyl group, a 1,1-dimethylpentyl group, a 1,1,2-trimethylbutyl group, a 1,1,3-trimethylbutyl group, a 1,1,2,2-tetramethylpropyl group, a 2,2-dimethylpentyl group, a 2,2,3-trimethylbutyl group, a 3-methylhexyl group, a 3,4-dimethylpentyl group, a 3,3-dimethylpentyl group, a 1-ethylpentyl group, a 1-ethyl-2-methylbutyl group, a 1-ethyl-3-methylbutyl group, a 1-ethyl-2,2-dimethylpropyl group, a 2-ethylpentyl group, a 2-ethyl-3-methylbutyl group, a 1-ethyl-1-methylbutyl group, a 1-ethyl-1,2-dimethylpropyl group, a 3-ethylpentyl group, a 1,1-diethylpropyl group, a 2,2-diethylpropyl group, a 1-propylbutyl group, a diisopropylmethyl group, and a 1-isopropylbutyl group. Among these, an alkyl group having 3 to 7 carbon atoms and having a branch is preferable, and a tert-butyl group is more preferable.

[0021] As the aliphatic hydrocarbon group, a branched alkyl group is more preferable, an alkyl group having 3 to 7 carbon atoms with a branch is even more preferable, and a tert-butyl group is particularly preferable, from the viewpoint that a graft-modified product excellent in adhesion strength to a substrate or layer having a polar group, particularly a substrate or layer containing polyester, can be easily obtained.

[0022] Examples of the alicyclic ring include monocyclic rings such as a cyclobutyl ring, a cyclopentyl ring, a cyclohexyl ring, and a cycloheptyl ring, polycyclic rings such as an adamantyl ring, and these rings having a hydrocarbon group such as an alkyl group as a substituent.

[0023] In formula (1), A is an alkanediyl group. The number of carbon atoms of the alkanediyl group is preferably 1 to 10, more preferably 2 to 6, and even more preferably 2 to 4. Examples of the alkanediyl group include a methanediyl group, an ethane-1,2-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. Among these, an ethane-1,2-diyl group is preferable.

[0024] In formula (1), m is an integer of 2 or more. From the viewpoints of the solubility of the carbodiimide compound (1) in a solvent, the availability of the raw material compound, and the ease of purification of the graft-modified product, etc., m is preferably an integer of 2 to 6, more preferably an integer of 2 to 4, and particularly preferably 2.

[0025] In formula (1), n is an integer of 1 or more from the viewpoints of being able to easily synthesize a graft-modified product capable of forming a layer with high adhesive strength on a substrate or layer having a polar group even in a short time. From the viewpoints of the solubility of the carbodiimide compound (1) in a solvent, the availability of raw material compounds, and the ease of purification of the graft-modified product, etc., n is preferably an integer of 1 to 6, more preferably an integer of 1 to 4, still more preferably 1 or 2, and particularly preferably 2 from the viewpoints of being able to easily obtain a graft-modified product having particularly excellent adhesive strength to a substrate or layer having a polar group.

[0026] As the carbodiimide compound (1), a compound represented by formula (1A) is preferable, and a compound represented by formula (1B) is particularly preferable.

Chemical formula

[0027] R in formula (1A) 1 , R 2 , m and n have the same meanings as the same symbols in formula (1) respectively. In formula (1B), R 1 is a hydrogen atom or a methyl group, preferably a methyl group, R 3 is a branched alkyl group, preferably a branched alkyl group having 3 to 7 carbon atoms, more preferably a tert-butyl group, n is an integer of 1 or more, preferably an integer of 1 to 6, more preferably an integer of 1 to 4, still more preferably 1 or 2, and particularly preferably 2.

[0028] The carbodiimide compound (1) can be used in various applications. For example, it can be suitably used as a monomer for graft modification for graft-modifying polymers such as polyolefins. However, the use of the carbodiimide compound (1) is not limited to the application of graft modification at all. For example, the carbodiimide compound (1) may be used as a polymerizable monomer for synthesizing a polymer. Examples of the above polymer include a homopolymer of one kind of carbodiimide compound (1), a copolymer of two or more kinds of carbodiimide compounds (1), and a copolymer of a carbodiimide compound (1) and another polymerizable monomer. Examples of other polymerizable monomers include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, and 4-methyl-1-pentene; cyclic olefins; conjugated polyenes; non-conjugated polyenes; vinyl compounds such as vinyl acetate; (meth)acrylic acid and its derivatives (for example, esters, salts, acid anhydrides).

[0029] The carbodiimide compound (1) can be produced, for example, by reacting a compound represented by the formula (1a) with an amine compound represented by the formula (1b) in the presence of a base as desired, or by reacting a compound represented by the formula (2a) with an isocyanate compound represented by the formula (2b) to obtain a urea compound, and then treating the urea compound with a dehydrating agent in the presence of a base as desired.

[0030] Examples of the base include pyridine, triethylamine, and N,N-diisopropylethylamine. Examples of the dehydrating agent include p-toluenesulfonyl chloride. The reaction temperature is, for example, -20 to 50°C. The reaction time varies depending on the raw material substances and the reaction temperature, but is, for example, 30 minutes to 3 days.

[0031]

Chemical formula

[0032] R in formula (1a) 1 , A, m, and n are synonymous with the same symbols in formula (1), respectively. R in formula (1b) 2 is synonymous with R in formula (1) 2 and is synonymous with it.

[0033] [Chemical formula]

[0034] R in formula (2a) 1 , A, m, and n are synonymous with the same symbols in formula (1), respectively. R in formula (2b) 2 is synonymous with R in formula (1) 2 and is synonymous with it.

[0035] As the compound represented by formula (1a), any of a biomass-derived compound, a fossil fuel-derived compound, and a mixture of both may be used. As the amine compound represented by formula (1b), any of a biomass-derived compound, a fossil fuel-derived compound, and a mixture of both may be used. As the compound represented by formula (2a), any of a biomass-derived compound, a fossil fuel-derived compound, and a mixture of both may be used. As the isocyanate compound represented by formula (2b), any of a biomass-derived compound, a fossil fuel-derived compound, and a mixture of both may be used. Using a biomass-derived compound or a mixture of a biomass-derived compound and a fossil fuel-derived compound is preferable from the viewpoint of reducing the environmental impact (mainly reducing greenhouse gas emissions).

[0036] [Graft modified product] Hereinafter, the graft modified product of the present disclosure will be described. The graft-modified product of the present disclosure is a graft-modified product of at least one base polymer selected from polyolefins with a carbodiimide compound (1). In other words, at least one base polymer selected from polyolefins is a polymer graft-modified with a carbodiimide compound (1). The graft-modified product includes, for example, a portion composed of at least one base polymer selected from polyolefins and a graft portion derived from the carbodiimide compound (1). The graft-modified product usually has a carbodiimide group derived from the carbodiimide compound (1).

[0037] The carbodiimide monomer used for graft-modifying the base polymer is at least the carbodiimide compound (1). The carbodiimide compound (1) may be one kind or two or more kinds, but preferably one kind. In graft modification, a modifying monomer other than the carbodiimide compound (1) (for example, a carbodiimide monomer having a carbodiimide group and a polymerizable double bond other than the carbodiimide compound (1)) may be used, but it is preferable to use only the carbodiimide compound (1) as the modifying monomer.

[0038] By using the graft-modified product of the present disclosure, a layer with high adhesive strength can be formed in a short time on a base material or layer having a polar group, including polymers such as polyester and polyphenylene sulfide. The graft-modified product of the present disclosure has high reactivity with the polar groups of polymers such as polyester or polyphenylene sulfide compared to the graft-modified product with glycidyl (meth)acrylate, and thus has excellent adhesion to a base material or layer containing such a polymer.

[0039] Since the graft-modified product of the present disclosure is a graft-modified product of polyolefin with a carbodiimide compound (1), rather than a block copolymer or a random copolymer of olefin monomers such as ethylene and propylene and the carbodiimide compound (1), the above effects are achieved well.

[0040] The grafting ratio of the carbodiimide compound (1) in the graft-modified product of the present disclosure is preferably 0.3 to 7% by mass, more preferably 0.5 to 5% by mass, in terms of the ease of synthesizing the graft-modified product and the ability to easily obtain a graft-modified product with excellent compatibility and adhesiveness, and also in terms of the fact that the resulting graft-modified product does not become too hard. The grafting ratio is the mass of the structure derived from the carbodiimide compound (1) in the graft-modified product, 1 and is determined by 1H-NMR measurement (specifically, the method described in the Examples section below).

[0041] <Base polymer> The base polymer, which is the object to be graft-modified by the carbodiimide compound (1), is at least one polymer selected from polyolefins.

[0042] A polyolefin is a polymer of an olefin. Examples of the olefin include α-olefins. The number of carbon atoms of the α-olefin is preferably 2 to 20, more preferably 2 to 12, and still more preferably 2 to 8. Examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, and 4-methyl-1-pentene.

[0043] The polyolefin may be a homopolymer of one kind of olefin or a copolymer of two or more kinds of olefins. The polyolefin may be a homopolymer of one kind of α-olefin, a copolymer of two or more kinds of α-olefins, or a copolymer of one or more kinds of α-olefins and one or more other monomers other than α-olefins. Examples of the other monomer include conjugated polyenes.

[0044] The polyolefin may be a polymer obtained using only raw materials derived from biomass (e.g., olefins), only raw materials derived from fossil fuels, or a polymer obtained using both raw materials derived from biomass and raw materials derived from fossil fuels. It is preferable from the viewpoint of reducing environmental impact (mainly reducing greenhouse gas emissions) that the polyolefin is a polymer obtained using raw materials derived from biomass.

[0045] In this specification, the raw material derived from biomass is any (renewable) natural raw material and its residue, such as those derived from plants or animals, including fungi, yeasts, algae, or bacteria, etc., and is used as a raw material. For example, as carbon 14 contains C isotopes at a ratio of about 1×10 -12 and the biomass carbon concentration (unit: pMC) measured in accordance with ASTM D6866 is about 100 pMC. The raw material derived from biomass can be obtained, for example, by conventionally known methods.

[0046] For a certain polymer, if the manufacturing conditions of the polymer, such as the polymerization catalyst, polymerization process, and polymerization temperature, are the same, even if it is a polymer obtained using raw materials derived from biomass, 14 except for containing C isotopes at a ratio of 1×10 -12 to 1×10 -14 the molecular structure is equivalent to that of a polymer obtained using raw materials derived from fossil fuels. Therefore, it is considered that the performance of a polymer obtained using raw materials derived from biomass and a polymer obtained using raw materials derived from fossil fuels does not change.

[0047] As the polyolefin, at least one polymer selected from ethylene-based polymers, propylene-based polymers, and butene-based polymers is preferable. When a solvent is used during the graft reaction, from the viewpoints of excellent solubility in the solvent and excellent separability between the graft-modified product and impurities after the graft reaction, as the polyolefin, at least one polymer selected from ethylene-based polymers and propylene-based polymers is more preferable.

[0048] The ethylene-based polymer is not particularly limited as long as the content ratio of the structural unit derived from ethylene in the polymer is 50% by mass or more, and it may be a homopolymer of ethylene or a copolymer of ethylene and a comonomer. In the case of a copolymer, its structure is not particularly limited.

[0049] Examples of the comonomer include at least one monomer selected from propylene, α-olefins having 4 to 20 carbon atoms, and conjugated polyenes. Among these, propylene and α-olefins having 4 to 20 carbon atoms are preferred. The α-olefins having 4 to 20 carbon atoms may be linear or branched, and examples thereof include 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

[0050] The content ratio of the structural unit derived from the comonomer in the ethylene-based polymer is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less from the viewpoints of small blocking of pellets and powders and easy handling. Note that an ethylene-based polymer in which the content ratio of the structural unit derived from propylene or butene is 50% by mass is classified as an ethylene-based polymer in this specification.

[0051] The propylene-based polymer is not particularly limited as long as the content ratio of the structural unit derived from propylene in the polymer is 50% by mass or more, and it may be a homopolymer of propylene or a copolymer of propylene and a comonomer. The structures of these polymers are not particularly limited.

[0052] Examples of the comonomer include at least one monomer selected from ethylene, α-olefins having 4 to 20 carbon atoms, and conjugated polyenes. Among these, ethylene and α-olefins having 4 to 20 carbon atoms are preferred. Examples of the α-olefins having 4 to 20 carbon atoms include the α-olefins having 4 to 20 carbon atoms described in the explanation of the ethylene-based polymer.

[0053] From the viewpoints such as small blocking of pellets and powders and easy handling, the content ratio of the structural unit derived from the comonomer in the propylene-based polymer is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less. Note that a propylene-based polymer in which the content ratio of the structural unit derived from butene is 50% by mass is classified as a propylene-based polymer in this specification.

[0054] The butene-based polymer is not particularly limited as long as the content ratio of the structural unit derived from butene in the polymer is 50% by mass or more, and may be a homopolymer of butene, particularly 1-butene, or a copolymer of butene (particularly 1-butene) and a comonomer. The structure of these polymers is not particularly limited.

[0055] Examples of the comonomer include at least one monomer selected from ethylene, propylene, α-olefins having 5 to 20 carbon atoms, and conjugated polyenes. Among these, ethylene, propylene, and α-olefins having 5 to 20 carbon atoms are preferred. Examples of the α-olefins having 5 to 20 carbon atoms include the α-olefins having 5 to 20 carbon atoms among the α-olefins described in the explanation of the ethylene-based polymer.

[0056] From the viewpoints such as small blocking of pellets and powders and easy handling, the content ratio of the structural unit derived from the comonomer in the butene-based polymer is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

[0057] The base polymer may be one type or two or more types, but preferably one type.

[0058] The base polymer is preferably a polymer having no active hydrogen-containing group selected from a carboxy group, an acid anhydride group, an amino group, a hydroxy group, and a thiol group, from the viewpoint that the above-described effects are more effectively exhibited.

[0059] The base polymer is also preferably a polymer having no group that can be easily converted into a group having active hydrogen, such as a carboxylic acid derivative group such as an acid halide, an amide, an imide, an ester, or an epoxy group, from the viewpoint that the above-described effects are more effectively exhibited.

[0060] The weight average molecular weight (Mw) of the base polymer is not particularly limited, but from the viewpoint of ease of synthesis of the graft-modified product, etc., it is preferably 100,000 or more, more preferably 150,000 or more, preferably 1,000,000 or less, more preferably 700,000 or less, and for example, it is 100,000 to 1,000,000.

[0061] The number average molecular weight (Mn) of the base polymer is not particularly limited, but from the viewpoint of ease of synthesis of the graft-modified product, etc., it is preferably 40,000 or more, more preferably 50,000 or more, preferably 500,000 or less, more preferably 300,000 or less, and for example, it is 40,000 to 500,000.

[0062] The molecular weight distribution (Mw / Mn) of the base polymer is not particularly limited, but it is preferably 1.5 or more, more preferably 2.0 or more, preferably 6.0 or less, more preferably 5.0 or less, and for example, it is 1.5 to 6.0.

[0063] Mw and Mn are values measured under the following conditions using a gel permeation chromatograph (GPC) of the HLC-8321 GPC / HT type manufactured by Tosoh Corporation. Separation column: TSKgel GMH 6 -HT (2 pieces) and TSKgel GMH 6 -HTL (2 pieces) (both 7.5 mm I.D. × 30 cm, manufactured by Tosoh Corporation) Column temperature: 140 °C Mobile phase: o-dichlorobenzene (containing 0.025% dibutylhydroxytoluene (BHT)) Developing rate: 1.0 mL / min Sample concentration: 0.1% (w / v) Sample injection volume: 0.4 mL Detector: differential refractometer Calibration of the apparatus: Use monodisperse polystyrene (manufactured by Tosoh Corporation, #3std set).

[0064] The base polymer can be synthesized by a conventionally known method or a commercially available product may be used. Examples of the conventionally known method include a method using a coordination polymerization catalyst containing a transition metal. Specifically, a method of synthesizing a base polymer by polymerizing a monomer such as the above-mentioned olefin in the presence of a catalyst such as a magnesium chloride-supported titanium catalyst, a vanadium-based catalyst containing a soluble vanadium compound and an alkylaluminum halide compound, or a metallocene catalyst containing a metallocene compound and an organoaluminum oxy compound can be mentioned.

[0065] <Synthesis method of graft-modified product> The synthesis method of the graft-modified product is not particularly limited. From the viewpoint of easily synthesizing the graft-modified product, a method of adding a radical initiator and a carbodiimide compound (1) to a solution in which the base polymer is dissolved or dispersed in a solvent, preferably a solution in which the base polymer is dissolved in an organic solvent, and reacting (graft reaction) is preferable. When using a reaction apparatus having a stirring ability capable of flowing the base polymer homogeneously, a solvent may not be used. According to the above method, since graft polymerization occurs, a graft-modified product can be obtained.

[0066] The amount of the carbodiimide compound (1) used in the graft reaction is preferably 10 to 1000 mol, more preferably 10 to 800 mol, per 1 mol of the base polymer, from the viewpoint of easily obtaining a graft-modified product having a graft ratio in the above range and suppressing the formation of a polymer of the carbodiimide compound (1) itself (hereinafter also referred to as "non-grafted polymer").

[0067] Examples of the radical initiator include organic peroxides and azo compounds. Examples of the organic peroxide include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxybenzoate)hexyne-3, 1,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate, tert-butyl perdiethylacetate, and tert-butyl peroxyisopropyl monocarbonate. Examples of the azo compound include azobisisobutyronitrile and dimethyl azoisobutyrate.

[0068] As the radical initiator, an organic peroxide is preferable, and dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,4-bis(tert-butylperoxyisopropyl)benzene, and tert-butyl peroxyisopropyl monocarbonate are more preferable.

[0069] The radical initiator may be used alone or in combination of two or more.

[0070] The amount of the radical initiator used in the graft reaction is preferably 0.01 mol or more, more preferably 0.05 mol or more, and preferably 0.7 mol or less, more preferably 0.5 mol or less, based on 1 mol of the carbodiimide compound (1), for example, 0.01 to 0.7 mol, from the viewpoints such as the graft reaction can occur efficiently and a graft-modified product having a graft ratio within the above range can be easily obtained.

[0071] As the organic solvent, an organic solvent that does not significantly inhibit the graft reaction of the carbodiimide compound (1) and has an affinity with the base polymer in the temperature range where the graft reaction is carried out is preferred. Specific examples of such organic solvents include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and decahydronaphthalene, chlorinated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, and tetrachloroethylene, alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and tert-butanol, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester solvents such as ethyl acetate and dimethyl phthalate, and ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran, and dioxyanisole. In addition, suspension polymerization and emulsion polymerization can also be carried out using water as the solvent. These solvents may be used alone or in combination of two or more. By using these solvents, it is preferable that the reaction solution becomes a homogeneous phase, but it may also be a heterogeneous plurality of phases.

[0072] In order to carry out the graft reaction in a region where the liquid containing the base polymer can be homogeneously stirred, the concentration of the base polymer in the liquid is usually set to 50 to 500 g / L, but in order to achieve a high graft ratio, it is preferably 200 to 500 g / L.

[0073] The radical initiator and the carbodiimide compound (1) may initiate the graft reaction by adding them all at once to the liquid containing the base polymer (or the base polymer itself), but in order to achieve a high graft ratio, it is preferable to carry out the graft reaction by adding them sequentially over about 0.1 to 5 hours.

[0074] When adding the radical initiator and the carbodiimide compound (1) to the base polymer or the liquid in which the base polymer is dissolved or dispersed in a solvent, the order of addition thereof is not particularly limited. For example, when adding them sequentially as described above, the radical initiator may be added first and then the carbodiimide compound (1) may be added sequentially, or the carbodiimide compound (1) may be added first and then the radical initiator may be added sequentially.

[0075] The reaction temperature of the graft reaction is preferably 60°C or higher, more preferably 100°C or higher, preferably 200°C or lower, more preferably 160°C or lower, and is, for example, 60 to 200°C. The reaction time of the graft reaction is preferably 2 hours or longer, more preferably 3 hours or longer, preferably 10 hours or shorter, more preferably 8 hours or shorter, and is, for example, 2 to 10 hours.

[0076] The graft-modified product obtained by the graft reaction may be purified and isolated by using known methods such as filtration, centrifugation, reprecipitation operation and / or washing as necessary, by combining the used solvent, unreacted radical initiator and carbodiimide compound (1), and by-product ungrafted polymer. In this case, from the viewpoint of easily obtaining a graft-modified product having excellent compatibility and adhesiveness, etc., it is desirable to purify and isolate so that the content ratio of the ungrafted polymer contained in the graft-modified product is preferably 5% by mass or less, more preferably 2% by mass or less.

[0077] <Uses of the graft-modified product> The graft modifier of the present disclosure is excellent in compatibility with, for example, polar resins and compatibility with olefin polymers. Therefore, the graft modifier can be used, for example, as a compatibilizer in a composition containing a polar resin and an olefin polymer.

[0078] The graft modifier of the present disclosure is excellent in adhesiveness to, for example, metals, glass, paper, polar resins, and olefin polymers. Therefore, the graft modifier can be used, for example, as an adhesive for a substrate or layer containing these materials.

[0079] The graft modifier of the present disclosure is excellent in dispersibility in olefin polymers. Therefore, the graft modifier can be used, for example, by mixing with an olefin polymer to form an olefin resin composition.

[0080] Examples of the polar resin include polyesters such as polyethylene terephthalate, polyphenylene sulfide, polyamide, polyacetal, polycarbonate, poly(meth)acrylate, modified fluororesin, and biomass plastics.

[0081] Examples of the olefin polymer include homopolymers or copolymers of α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene (e.g., high-pressure low-density polyethylene, linear low-density polyethylene (LLDPE), medium-density polyethylene, high-density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, low-crystalline or amorphous ethylene-propylene random copolymer, ethylene-1-butene random copolymer, propylene-1-butene random copolymer), ethylene-vinyl acetate copolymer (EVA) or its saponified product, ethylene-(meth)acrylic acid copolymer or its metal salt (ionomer), ethylene-cyclic olefin copolymer, and polymers obtained by graft-modifying these polymers with polar compounds such as maleic acid and silane compounds.

[0082] Since the graft-modified product of the present disclosure is excellent in adhesion to polyester or polyphenylene sulfide, it is preferably used as an adhesive or an olefin resin composition for polyester or polyphenylene sulfide, or an adhesive or an olefin resin composition for a substrate or layer containing polyester or polyphenylene sulfide, in terms of more effectively exhibiting the above effects.

[0083] When using the graft-modified product of the present disclosure for various applications, other components such as various additives may be blended with the graft-modified product as necessary within a range that does not impair the object of the present disclosure. Examples of other components such as additives include softeners, stabilizers, fillers, antioxidants, crystal nucleating agents, waxes, thickeners, mechanical stability imparting agents, leveling agents, wetting agents, film-forming aids, crosslinking agents, preservatives, rust preventives, pigments, dispersants, antifreeze agents, defoaming agents, tackifiers, other thermoplastic polymers, water, and organic solvents. These may be used individually or in combination of two or more.

[0084] [Olefin resin composition] The olefin resin composition of the present disclosure contains the above-described graft-modified product of the present disclosure and an olefin polymer. The graft-modified product of the present disclosure contained in the olefin resin composition may be one kind or two or more kinds. The olefin polymer contained in the olefin resin composition may be one kind or two or more kinds.

[0085] Since the above olefin resin composition contains the graft-modified product of the present disclosure, a layer with high adhesive strength can be formed in a short time on a substrate or layer having a polar group.

[0086] The content ratio of the graft-modified product of the present disclosure in the above olefin resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, particularly preferably 5% by mass or more, from the viewpoints of moldability, adhesiveness, and economy, etc., and is preferably 40% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, for example, 0.5 to 40% by mass.

[0087] The olefin-based polymer is not particularly limited as long as it is a polymer mainly composed of olefins, and various known olefin-based polymers can be used. Examples of the olefin-based polymer include the olefin-based polymers described in the use column of the graft-modified product. The olefin-based polymer is preferably the same polymer as the base polymer used in the synthesis of the above graft-modified product from the viewpoints of excellent compatibility between the above graft-modified product and the olefin-based polymer and being able to easily obtain a composition in which the desired effects are more exerted.

[0088] The content ratio of the olefin-based polymer in the above olefin resin composition is preferably 60% by mass or more, more preferably 75% by mass or more, still more preferably 80% by mass or more, and preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 97% by mass or less, particularly preferably 95% by mass or less, from the viewpoints of moldability, adhesiveness, and economy, etc., and is, for example, 60 to 99.5% by mass.

[0089] The above olefin resin composition may further contain other components such as additives. The other components such as additives may be one kind or two or more kinds. Specific examples of the other components such as additives are as described above.

[0090] In one embodiment, the amount of carbodiimide groups in the above olefin resin composition is preferably 0.1 to 50 mmol, more preferably 0.2 to 20 mmol, and even more preferably 0.5 to 5 mmol per 100 g of the resin composition. A resin composition having a carbodiimide group amount within the above range tends to adhere firmly even when adhering to a substrate or layer having a polar group at a low temperature. Specifically, the above amount of carbodiimide groups is calculated by the method described in the following Examples section.

[0091] In one embodiment, the density of the above olefin resin composition is preferably 0.870 to 0.940 g / cm 3 , more preferably 0.880 to 0.925 g / cm 3 and even more preferably 0.890 to 0.920 g / cm 3 A resin composition having a density within the above range tends to adhere firmly even when adhering to a substrate or layer having a polar group at a low temperature. The above density is measured at 23°C in accordance with JIS K 7112-2:2023 (density gradient tube method).

[0092] The melt flow rate (MFR) of the above olefin resin composition is preferably 0.1 to 10 g / 10 min, more preferably 0.2 to 5 g / 10 min. A resin composition having an MFR within the above range tends to be able to easily form a desired layer. The MFR is measured under the conditions of 190°C and a load of 2.16 kg in accordance with Method A of JIS K 7210-1:2014.

[0093] In addition to being used as an adhesive (adhesive resin composition), the above olefin resin composition can also be used, for example, as printing ink, paint, a machine cleaner for polymer processing, or a binder.

[0094] [Adhesive] The adhesive of the present disclosure is not particularly limited as long as it contains the graft-modified product or the olefin resin composition of the present disclosure described above, and the graft-modified product or the olefin resin composition contained in the adhesive may be one kind or two or more kinds. In the present specification, the term "adhesive" is used in the meaning including a pressure-sensitive adhesive.

[0095] The above-mentioned adhesive may be, for example, an adhesive composed of a graft-modified product, an adhesive composed of a graft-modified product and other components such as additives, or an adhesive composed of an olefin resin composition. The above-mentioned adhesive may further contain other components such as additives. The other components such as additives may be one kind or two or more kinds. Specific examples of the other components such as additives are as described above.

[0096] The content ratio of the graft-modified product of the present disclosure in the above-mentioned adhesive is preferably 5 to 100% by mass, more preferably 10 to 100% by mass.

[0097] The above-mentioned adhesive can be used in various known forms, for example, as a water-dispersion type adhesive, an organic solvent type adhesive, or a hot-melt type adhesive. Examples of the adhesion target of the above-mentioned adhesive include layers made of metal, glass, wood, paper, or cloth, layers containing a thermoplastic resin, layers containing a thermosetting resin, and layers containing a cured resin of a thermosetting resin. Specific examples of the thermoplastic resin and the thermosetting resin will be described later.

[0098] [Laminate] The laminate of the present disclosure has a layer (A) selected from the layer containing the graft-modified product of the present disclosure and the layer containing the olefin resin composition of the present disclosure, and a base material layer (B). In the present specification, when referring to the base material contained in the laminate, it is described as "base material layer".

[0099] The laminate may have two or more layers of layer (A) and may also have two or more layers of base material layer (B). When the laminate has two or more layers of layer (A), these layers may be the same layer or different layers. When the laminate has two or more layers of base material layer (B), these layers may be the same layer or different layers.

[0100] The laminate is preferably a laminate having layer (A) and base material layer (B), or a laminate having base material layer (B), layer (A), and base material layer (B) in this order. The laminate 1 shown in FIG. 1 has layer (A) 10 and base material layer (B) 20. The laminate 1 shown in FIG. 2 has a first base material layer (B) 21, layer (A) 10, and a second base material layer (B) 22 in this order.

[0101] Layer (A) can be formed, for example, using the graft-modified product, adhesive, or olefin resin composition of the present disclosure described above respectively. Whether the graft-modified product is contained in layer (A) can be determined by infrared spectroscopic analysis.

[0102] Examples of the base material layer (B) include a layer containing materials such as metal, glass, wood, paper, cloth, thermoplastic resin, thermosetting resin, and rubber, or a layer formed from these materials. Specifically, a layer made of metal, glass, wood, paper, or cloth, a layer containing a thermoplastic resin, a layer containing a thermosetting resin, and a layer containing a cured resin of a thermosetting resin are included.

[0103] Examples of the thermoplastic resin include olefin polymers (e.g., the same polymers as those listed in the use column of the graft-modified product), polystyrene, acrylonitrile-butadiene-styrene copolymer, polyacrylonitrile, polyester (e.g., polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate), polyphenylene sulfide, polyketone, polyamide (e.g., nylon-6, nylon-66, polymetaxylylene adipamide), poly(meth)acrylate (e.g., polymethyl methacrylate), polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, thermoplastic polyimide, thermoplastic polyurethane, polyvinyl alcohol, polyacetal, polycarbonate, biodegradable plastics (e.g., aliphatic polyesters such as polylactic acid), modified fluororesin, biomass plastics (e.g., starch resin), liquid crystal polymer, and other engineering plastics. Among these, polar resins are preferred, and polyester and polyphenylene sulfide are preferred.

[0104] Examples of the thermosetting resin include epoxy resin, unsaturated polyester resin, phenol resin, urea-melamine resin, polyurethane resin, silicone resin, and thermosetting polyimide.

[0105] The base material layer (B) preferably has a polar group. Since the carbodiimide group in the graft-modified product in the layer (A) reacts with the polar group in the base material layer (B) and is in a bonded state, the adhesiveness between the layer (A) and the base material layer (B) is further improved. In this case, the layer (A) contains not only the graft-modified product but also a polymer in which the carbodiimide group in the graft-modified product reacts with the polar group in the base material layer (B).

[0106] Examples of the polar group include a carboxy group, a hydroxy group, an amino group, an ester group, and a carbonyl group. Among these, a carboxy group and a hydroxy group are preferable. The base material layer (B) may have two or more kinds of polar groups. For example, a polyester usually has a carboxy group and / or a hydroxy group at its terminal. Also, polyphenylene sulfide usually has a carboxy group at its terminal. Glass and metal also usually have a hydroxy group.

[0107] The base material layer (B) such as a layer containing a thermoplastic resin, a layer containing a thermosetting resin, and a layer containing a cured resin of a thermosetting resin may contain an additive within a range not impairing the object of the present invention, if necessary. Examples of the additive include a phenolic antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a metal compound, and a metal salt of a higher fatty acid, which are usually added to a resin and used. The additive may be one kind or two or more kinds.

[0108] The thickness of the layer (A) is not particularly limited and may be appropriately selected according to the use of the laminate, but is preferably 2 to 1000 μm. The thickness of the base material layer (B) is not particularly limited and may be appropriately selected according to the use of the laminate, but is preferably 2 to 1000 μm.

[0109] The above laminate is not limited to a laminated film (sheet) shape and may be any of various known shapes such as a hollow container, a cup, and a tray.

[0110] The method for producing the above laminate varies depending on the shape, size, required physical properties, etc. of the final product and is not particularly limited. For example, the following methods (1) to (4) can be mentioned. (1) A method of thermally fusing both of them using a calender roll forming machine, a compression molding machine, etc. at a temperature equal to or higher than the temperature at which at least one of the pre-formed layer (A) and the base material layer (B) melts. (2) A method of thermally fusing a pre-formed layer (A) or the base material layer (B) to another layer by extrusion molding or calender molding. (3) When using a layer containing a thermoplastic resin as the base material layer (B), a method of simultaneously extruding and thermally fusing (co-extrusion molding) the layer (A) and the base material layer (B) using a multi-layer extrusion molding machine. (4) When using a layer containing a thermoplastic resin as the base material layer (B), a method of injecting the molten layer (A) forming material and the molten base material layer (B) forming material into a mold with a shifted injection timing (e.g., two-layer injection molding, sandwich injection molding).

[0111] Since the laminate has a layer (A) containing a graft-modified product or an olefin resin composition, it has excellent interlayer adhesion. Even when the laminate is heat-treated at a high temperature of, for example, 200 to 250 °C, the interlayer adhesive force tends to be less likely to decrease. For example, when thermally fusing the layer (A) and the base material layer (B) at 200 °C, even if the heat-sealing time is set to a short time of preferably 20 seconds or less, more preferably 10 seconds or less, and even more preferably 5 seconds or less, a laminate with high interlayer adhesion strength can be formed.

[0112] [Aspect Example] The present disclosure relates to, for example, the following [1] to

[10] . [1] A carbodiimide compound represented by the following formula (1). [Chemical Formula] [In formula (1), R 1 is a hydrogen atom or a methyl group, R 2 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, A is an alkanediyl group, m is an integer of 2 or more, and n is an integer of 1 or more.] [2] The carbodiimide compound according to [1], wherein R 1 is a methyl group, R 2 is a branched alkyl group, A is an ethane-1,2-diyl group, and m is 2. [3] A graft-modified product of at least one base polymer selected from polyolefins with the carbodiimide compound according to [1] or [2]. [4] The graft-modified product according to [3] above, wherein the polyolefin is at least one selected from an ethylene-based polymer and a propylene-based polymer. [5] The graft-modified product according to [3] or [4] above, wherein the base polymer is a polymer having none of a carboxy group, an acid anhydride group, an amino group, a hydroxy group, and a thiol group. [6] An olefin-based resin composition containing the graft-modified product according to any one of [3] to [5] above and an olefin-based polymer. [7] An adhesive containing the graft-modified product according to any one of [3] to [5] above or the olefin-based resin composition according to [6] above. [8] A laminate having a layer (A) selected from a layer containing the graft-modified product according to any one of [3] to [5] above and a layer containing the olefin-based resin composition according to [6] above, and a base material layer (B). [9] The laminate according to [8] above, wherein the base material layer (B) is a layer having a polar group.

[10] The laminate according to [9] above, wherein the polar group is at least one selected from a carboxy group and a hydroxy group.

Examples

[0113] Hereinafter, the carbodiimide compound and the like of the present disclosure will be described more specifically by examples, but the carbodiimide compound and the like of the present disclosure are not limited to the examples.

[0114] [Structure of Carbodiimide Compound] The structure of the carbodiimide compound is 1 identified by an H-NMR spectrum (400 MHz, apparatus name: ECZ400S, manufactured by JEOL Ltd.).

[0115] [Graft Ratio] The grafting ratio in the graft-modified product was calculated by the method described below. Using a Bruker Biospin Corporation AVANCEIIIcryo-500 nuclear magnetic resonance apparatus (500 MHz), the measurement solvent: 1,1,2,2-tetrachloroethane-d2, the measurement temperature: 120 °C, the spectral width: 20 ppm, the pulse repetition time: 7.0 seconds, and the pulse width: 5.00 μsec (45° pulse), 1 the 1H-NMR spectrum was measured. In the obtained spectrum, the grafting ratio (mass %) was calculated from the peak intensity ratio between the protons of the hydrocarbon group bonded to the carbodiimide group, which is present at 3.0 ppm to 4.0 ppm, and the protons bonded to all the hydrocarbon groups derived from the base polymer, which are present at 0.3 ppm to 2.5 ppm.

[0116] [Amount of carbodiimide group] The amount (mmol) of the carbodiimide group per 100 g of the adhesive composition was calculated from the following formula (I). The results are shown in Table 1 as the amount of carbodiimide group (mmol / 100 g). (Grafting ratio [mass %] of the graft-modified product used in the adhesive composition / molecular weight of the carbodiimide monomer used in the synthesis of the graft-modified product) × 100 × amount [mass %] of the graft-modified product used in the adhesive composition / 10 ··· (I)

[0117] [Density] The density (g / cm 3 ) of the adhesive composition was measured at 23 °C in accordance with JIS K 7112-2:2023 (density gradient tube method).

[0118] [MFR] The MFR (g / 10 min) of the adhesive composition was measured under the conditions of 190 °C and a load of 2.16 kg in accordance with Method A of JIS K 7210-1:2014.

[0119] [Example 1A] A glass container was charged with 4.04 g of tert-butylamine, 44 g of pyridine, and a stir bar, and the inside of the container was purged with nitrogen. The stir bar was rotated using a magnetic stirrer to stir the liquid inside the container, and while cooling with an ice bath, 11.0 g of Karenz (registered trademark) MOI-EG (manufactured by Resonac Co., Ltd., 2-(2-methacryloyloxyethyloxy)ethyl isocyanate) was added dropwise. After the addition, the ice bath was removed, and the liquid inside the container was stirred at room temperature for 1 hour, and then 11.5 g of p-toluenesulfonyl chloride was charged. After stirring the liquid inside the container for 19 hours, 50 g of water was charged while cooling with an ice bath.

[0120] Thereafter, using a separatory funnel, an operation of adding a mixed solution of 35 g of ethyl acetate and 15 g of hexane, separating the layers, and extracting the organic layer from the aqueous layer was repeated 5 times. 40 g of water was added to the obtained organic layer, the layers were separated, and an operation of discarding the aqueous layer was repeated 5 times. The obtained organic layer was dried over sodium sulfate. The sodium sulfate was removed by filtration, the solvent was distilled off using an evaporator, and then the residue was purified by a silica gel column to obtain 6.41 g (yield 46%) of a carbodiimide compound. 1 By structural analysis using H-NMR, it was confirmed that the obtained carbodiimide compound was a compound represented by the following formula (ethoxyethyl-tert-butylcarbodiimide methacrylate). 1 H-NMR (CDCl 3 , ppm): 1.28 (s, CH 3 ×3), 1.95 (dd, CH 3 ), 3.36 - 3.39 (t, CH 2 ), 3.60 - 3.63 (t, CH 2 ), 3.73 - 3.76 (m, CH 2 ), 4.29 - 4.32 (m, CH 2 ), 5.58 (quin, CH), 6.14 (sext, CH)

[0121]

Chemical formula

[0122] [Example 2A] Into the vessel of the Dean-Stark apparatus, 19.7 g of paratoluenesulfonic acid monohydrate, 47 g of toluene, 14.0 g of 2-[2-(2-aminoethoxy)ethoxy]ethanol, and a stir bar were charged, and the inside of the vessel was purged with nitrogen under light shielding. Using a magnetic stirrer, the stir bar was rotated, and the liquid in the vessel was stirred for 15 minutes. 12.1 g of methacrylic acid and 40 mg of phenothiazine were charged, and the mixture was stirred under heating under reflux for 6 hours. The liquid was cooled to room temperature, the solvent was distilled off using an evaporator, and the residue was dissolved in 695 g of dichloromethane to obtain a dichloromethane solution.

[0123] Into a glass vessel, the above dichloromethane solution, 17.0 g of N,N-diisopropylethylamine, and a stir bar were charged, and the inside of the vessel was purged with nitrogen. Using a magnetic stirrer, the stir bar was rotated, the liquid in the vessel was stirred, and 6.50 g of tert-butyl isocyanate was added dropwise while cooling in an ice bath. After the addition dropwise, the ice bath was removed, and the liquid in the vessel was stirred for 1 hour. After distilling off the solvent using an evaporator, the residue was purified by a silica gel column to obtain 14.7 g (yield 89%) of the urea compound.

[0124] Into a glass vessel, 13.5 g of the above urea compound, 34 g of pyridine, and a stir bar were charged, and the inside of the vessel was purged with nitrogen. Using a magnetic stirrer, the stir bar was rotated, the liquid in the vessel was stirred, and 8.94 g of p-toluenesulfonyl chloride was charged. After stirring the liquid in the vessel at room temperature for 16 hours, 50 g of water was added while cooling in an ice bath.

[0125] Thereafter, using a separatory funnel, a mixture of 35 g of ethyl acetate and 15 g of hexane was added, liquid separation was carried out, and the operation of extracting the organic layer from the aqueous layer was repeated 5 times. 40 g of water was added to the obtained organic layer, liquid separation was carried out, and the operation of discarding the aqueous layer was repeated 5 times. The obtained organic layer was dried over sodium sulfate. Sodium sulfate was removed by filtration, the solvent was distilled off using an evaporator, and the residue was purified by a silica gel column to obtain 8.70 g (yield 69%) of the carbodiimide compound. 1By structural analysis using H-NMR, it was confirmed that the obtained carbodiimide compound was a compound represented by the following formula (methacrylic acid diethylene glycol monoethyl ether-tert-butyl carbodiimide). 1 H-NMR (DMSO-d6, ppm): 1.21 (s, CH 3 ×3), 1.88 (dd, CH 3 ), 3.24 - 3.27 (t, CH 2 ), 3.50 - 3.53 (t, CH 2 ), 3.53 - 3.59 (m, CH 2 ×2), 3.65 - 3.67 (m, CH 2 ), 4.20 - 4.22 (m, CH 2 ), 5.69 (quin, CH), 6.03 (sext, CH)

[0126] [Chemical Formula]

[0127] [Example 1B] A 500 mL separable flask was charged with 16.0 g of polypropylene (base polymer, propylene homopolymer, Mw: 313,000, Mn: 70,800, Mw / Mn: 4.42) and 35 mL of xylene, and the inside of the separable flask was purged with nitrogen. Then, the internal temperature of the separable flask was raised to 120 °C, and while maintaining this temperature, 16 mmol of ethoxyethyl-tert-butyl carbodiimide methacrylate was charged. Next, 6.5 mmol of tert-butyl peroxyisopropyl monocarbonate (Perbutyl I, manufactured by NOF Corporation) dissolved in 10 mL of xylene was fed over 10 minutes while stirring at a stirring speed of 400 rpm using a double anchor blade. Then, after further stirring for 3 hours, 200 mL of xylene was fed to dilute the reaction solution.

[0128] Thereafter, the internal temperature of the separable flask was lowered to 50 °C, and the slurry-like reaction solution was taken out. 200 mL of acetone was added to the obtained reaction solution, and after stirring for 10 minutes, the solution after stirring was filtered to separate it into a solid content and a filtrate. The steps from adding this acetone to the obtained solid content to filtration were repeated 3 more times. By these 4 filtrations, unreacted ethoxyethyl methacrylate - tert - butylcarbodiimide and the homopolymer of ethoxyethyl methacrylate - tert - butylcarbodiimide were removed.

[0129] The solid content after the 4th filtration was dried in a vacuum dryer at 90 °C for 10 hours to obtain 16.35 g of the graft polymer (P - 1). The grafting rate was 1.7 mass%.

[0130] [Example 2B] A 500 mL separable flask was charged with 22.5 g of polypropylene (base polymer, propylene homopolymer, Mw: 313,000, Mn: 70,800, Mw / Mn: 4.42) and 62 mL of xylene, and the inside of the separable flask was purged with nitrogen. Thereafter, the internal temperature of the separable flask was raised to 120 °C, and while maintaining that temperature, 22.1 mmol of diethylene glycol monoethyl ether methacrylate - tert - butylcarbodiimide was charged. Then, 9.2 mmol of tert - butyl peroxyisopropyl monocarbonate (Perbutyl I, manufactured by NOF Corporation) dissolved in 10 mL of xylene was fed over 10 minutes while stirring at a stirring speed of 400 rpm using a double - anchor blade. Thereafter, after further stirring for 3 hours, 200 mL of xylene was fed to dilute the reaction solution.

[0131] Thereafter, the internal temperature of the separable flask was lowered to 50°C, and the slurry-like reaction solution was taken out. 300 mL of acetone was added to the obtained reaction solution, and after stirring for 10 minutes, the stirred solution was filtered and separated into a solid content and a filtrate. The steps from adding this acetone to the obtained solid content to filtration were repeated 3 more times. By these 4 filtrations, unreacted diethylene glycol monoethyl ether methacrylate-tert-butylcarbodiimide and the homopolymer of diethylene glycol monoethyl ether methacrylate-tert-butylcarbodiimide were removed.

[0132] The solid content after the 4th filtration was dried in a vacuum dryer at 90°C for 10 hours to obtain 23.25 g of the graft polymer (P-2). The grafting rate was 2.0 mass%.

[0133] [Reference Example 1B] A 500 mL glass container was charged with 15.0 g of polypropylene (the same polymer as the base polymer used in Example 1B) and 62 mL of xylene, and the inside of the container was purged with nitrogen. Thereafter, the internal temperature of the container was raised to 120°C, and while maintaining that temperature, 22.1 mmol of ethyl methacrylate-tert-butylcarbodiimide was charged. Then, 9.2 mmol of tert-butyl peroxyisopropyl monocarbonate (Perbutyl I, manufactured by NOF Corporation) dissolved in 10 mL of xylene was fed over 10 minutes while stirring at a stirring speed of 400 rpm using a double anchor blade. Thereafter, after further stirring for 3 hours, 150 mL of xylene was fed to dilute the reaction solution.

[0134] Thereafter, the internal temperature of the container was lowered to 50°C, and the slurry-like reaction solution was taken out. 400 mL of acetone was added to the obtained reaction solution, and after stirring for 10 minutes, the stirred solution was filtered and separated into a solid content and a filtrate. The steps from adding this acetone to the obtained solid content to filtration were repeated 3 more times.

[0135] The solid content after the fourth filtration was dried in a vacuum dryer at 90 °C for 10 hours to obtain 15.37 g of a graft polymer (P-3). The grafting ratio was 1.3 mass%.

[0136] [Example 1C] 11 parts by mass of the graft polymer (P-1) produced in Example 1B and 89 parts by mass of polypropylene (the same polymer as the base polymer used in Example 1B) were kneaded using a lab plastomill under the conditions of a temperature of 190 °C, a screw rotation speed of 60 rpm, and a kneading time of 10 minutes to obtain an adhesive composition. The obtained adhesive composition had an MFR (190 °C, 2.16 kg load) of 4.4 g / 10 min and a density of 0.899 g / cm 3 and the amount of carbodiimide groups per 100 g of the composition was 0.8 mmol.

[0137] [Example 2C] An adhesive composition was obtained in the same manner as in Example 1C, except that 12 parts by mass of the graft polymer (P-2) produced in Example 2B and 88 parts by mass of polypropylene (the same polymer as the base polymer used in Example 2B) were used. The obtained adhesive composition had an MFR (190 °C, 2.16 kg load) of 3.1 g / 10 min and a density of 0.901 g / cm 3 and the amount of carbodiimide groups per 100 g of the composition was 0.8 mmol.

[0138] [Reference Example 1C] An adhesive composition was obtained in the same manner as in Example 1C, except that 13 parts by mass of the graft polymer (P-3) produced in Reference Example 1B and 87 parts by mass of polypropylene (the same polymer as the base polymer used in Example 1B) were used. The obtained adhesive composition had an MFR (190 °C, 2.16 kg load) of 2.0 g / 10 min and a density of 0.892 g / cm 3 and the amount of carbodiimide groups per 100 g of the composition was 0.8 mmol.

[0139] [Comparative Example 1C] Lotader (manufactured by Arkema; density 0.940 g / cm3 、The amount of epoxy groups per 100 g of the composition was 56 mmol, and a composition for adhesion (not containing a graft-modified product with a carbodiimide monomer) was used.

[0140] [Adhesion evaluation] · Preparation of press sheet For each of the adhesion compositions obtained in Examples 1C to 2C, Reference Example 1C, and Comparative Example 1C, press molding was performed under the conditions of a temperature of 170 °C, a pressure of 4 MPa, a post-heating time of 8 minutes, and a pressurization time of 3 minutes. The obtained sheet was then rapidly cooled using a press molding machine set at 20 °C to prepare a press sheet having a length of 80 mm, a width of 80 mm, and a thickness of 500 μm.

[0141] · Preparation of laminate As the base material, two polyethylene terephthalate (PET) sheets (product name: Lumirror T60, manufactured by Toray Industries, Inc.) having a length of 80 mm, a width of 80 mm, and a thickness of 50 μm were used (the first PET sheet and the second PET sheet). The first PET sheet, the above press sheet, and the second PET sheet were stacked in this order, and the stacked sheets were sandwiched between two Teflon (registered trademark) sheets. Heat sealing was performed using a heat sealer with the temperature of the upper and lower press plates set at 200 °C under the conditions of a pressure of 0.15 MPa, a heat sealing time of 2 seconds, 3 seconds, or 5 seconds to prepare a three-layer laminate.

[0142] · Peel test For the prepared laminate, the first PET sheet (the PET sheet on the press plate (upper) side) and the press sheet were subjected to T-peel under the conditions of a peel atmosphere temperature of 23 °C, a peel rate of 300 mm / min, and a peel width of 15 mm to measure the peel strength (average peel strength) between the first PET sheet and the press sheet. The results are shown in Table 1. In addition, since the adhesive force was strong, the case where the PET sheet was cut instead of at the interface between the PET sheet and the press sheet was indicated as "PET resin cut".

[0143]

Table 1

[0144] From the results in Table 1, it can be seen that the press sheet formed from the adhesive composition of Comparative Example 1C is inferior in adhesiveness to the PET sheet, whereas the press sheets formed from the adhesive compositions of Reference Example 1C, Example 1C, and Example 2C are excellent in adhesiveness to the PET sheet. Also, compared with the press sheet formed from the adhesive composition of Reference Example 1C, the press sheets formed from the adhesive compositions of Example 1C and Example 2C are even more excellent in adhesiveness to the PET sheet and can exhibit more excellent adhesiveness even when the heat seal time is short.

Explanation of Signs

[0145] 1... laminate 10... layer (A) 20, 21, 22... base material layer (B)

Claims

1. A carbodiimide compound represented by the following formula (1). 【Chemical 1】 [In formula (1), R 1 is a hydrogen atom or a methyl group, R 2 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, A is an alkanediyl group, m is an integer of 2 or more, and n is an integer of 1 or more.]

2. The aforementioned R 1 is a methyl group, the aforementioned R 2 is a branched alkyl group, the aforementioned A is an ethane-1,2-diyl group, and m is 2. The carbodiimide compound according to claim 1.

3. A graft-modified product of at least one base polymer selected from polyolefins with the carbodiimide compound according to Claim 1.

4. The graft-modified product according to Claim 3, wherein the polyolefin is at least one selected from ethylene-based polymers and propylene-based polymers.

5. The graft-modified product according to Claim 3, wherein the base polymer is a polymer having none of a carboxy group, an acid anhydride group, an amino group, a hydroxy group, and a thiol group.

6. An olefin-based resin composition containing the graft-modified product according to Claim 3 and an olefin-based polymer.

7. An adhesive containing the graft-modified product according to Claim 3 or the olefin-based resin composition according to Claim 6.

8. A layer (A) selected from a layer containing the graft-modified product according to Claim 3 and a layer containing the olefin-based resin composition according to Claim 6, and a base material layer (B). A laminate having the above.

9. The laminate according to Claim 8, wherein the base material layer (B) is a layer having a polar group.

10. The laminate according to Claim 9, wherein the polar group is at least one selected from a carboxy group and a hydroxy group. ​

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