WO2023171709A1 - Resin composition and method for producing same - Google Patents

Abstract

Provided is a resin composition that, utilizing a host-guest interaction, exhibits an excellent elasticity while at the same time exhibiting an excellent toughness. The resin composition characteristically comprises a resin component (A) that has a host group and essentially contains another constituent unit based on a radically polymerizable monomer, and a polymer (B) obtained by the polymerization of radically polymerizable monomer in a solution of the resin component (A), wherein the host group is C1 (each R in the formula is independently a functional group selected from the group consisting of hydrogen, the acetyl group, alkyl groups having not more than 50 carbons, and -CONHR (R is a methyl group or ethyl group) and X = 5 to 7).

Description

Resin composition and method for producing the same

The present invention relates to a resin composition and a method for producing the same.

In recent years, development of supramolecular materials with various functionalities using cyclodextrin derivatives and utilizing non-covalent interactions typified by host-guest interactions has been actively conducted. For example, host group-containing polymerizable monomers have been proposed that have self-repairing properties and excellent elasticity, and host group-containing polymerizable monomers that use cyclodextrin derivatives as raw materials for the polymer materials (Patent Documents 1 to 4).

Furthermore, if the physical properties of such a resin composition can be improved, it is expected that its usable applications will be expanded.
Generally, resin compositions with excellent elasticity often have insufficient physical strength. For this reason, the above-mentioned supramolecular materials would also be highly desirable if their physical strength could be improved in addition to their stretchability.

Patent Document 5 and Non-Patent Documents 1 and 2 describe mixing micronized cellulose fibers with the supramolecular material. It is disclosed that this makes it possible to improve physical properties. It would be more preferable if the physical properties could be further improved based on such knowledge.

International Publication 2013/162019 International publication 2020/116590 International Publication 2021/045215 International publication 2022/024908 JP2021-70768A

APPLIED POLYMER MATERIALS 2020, 2, 2274-2283 Biomacromolecules 2020, 21, 3936-3944

An object of the present invention is to provide a resin composition that has excellent elasticity and toughness by utilizing host-guest interaction.

The present invention
A resin component (A) having a host group and essentially having a structural unit based on another radically polymerizable monomer, and
Containing a polymer (B) obtained by polymerizing a radically polymerizable monomer in a solution of the resin component (A),
The host group is

(wherein, R is the same or different and is a functional group X = 5 to 7 selected from the group consisting of hydrogen, an acetyl group, an alkyl group having 50 or less carbon atoms, and -CONHR (R is a methyl group or an ethyl group) )
This is a resin composition characterized by the following.

It is preferable that the resin component (A) further has a guest group.
The blending amounts of (A) and (B) are:
(A)/((A)+(B)) (weight ratio) is preferably 65 to 95% by weight.

Preferably, the resin composition further contains cellulose (C) modified with a compound having at least one functional group F selected from the group consisting of a carboxy group, a hydroxyl group, an amino group, and an amide group.

The blending amounts of (A) to (C) are:
(A)/((A)+(B)+(C))(weight ratio) is 57 to 95
(B)/((A)+(B)+(C))(weight ratio) is 4 to 35
(C)/((A)+(B)+(C))(weight ratio) is 1 to 16
It is preferable that

The resin component (A) is preferably a copolymer of a host group-containing monomer and another radically polymerizable monomer.

The present invention provides a step (1-1) of preparing a solution of resin component (A).
Step (1-2) of adding raw material monomers for polymer (B) to the solution obtained in step (1-1), and polymerizing the composition obtained in step (1-2). Process (1-3)
It is also a method for producing the above-mentioned resin composition, characterized by having the following.

Step (1-2) is preferably carried out in the presence of cellulose (C) modified with a compound having a functional group F.

The present invention provides a step (2-1) of producing a molded article containing a resin component (A).
Step (2-2) of impregnating the molded article obtained in step (2-1) with the raw material monomer of polymer (B) and impregnation with the monomer obtained in step (2-2). Step (2-3) of polymerizing monomers in the resin molding to obtain polymer (B)
It is also a method for producing the above-mentioned resin composition comprising:

Step (2-1) is preferably carried out in the presence of cellulose (C) modified with a compound having a functional group F.

The present invention also provides a resin molded product characterized by being made of the resin composition described above.
The resin molded article preferably has an elastic modulus of 5 to 60 MPa.
The resin molded product preferably has a toughness of 5 to 90 MJm-3 in a tensile test.

The resin composition of the present invention has both stretchability and toughness.

FIG. 2 is a schematic diagram showing the mechanism that produces the effects of the present invention. FIG. 1 is a schematic diagram showing a method for synthesizing a resin composition of the present invention. FIG. 3 is a diagram showing the results of Example 1. FIG. 3 is a diagram showing the results of Example 2. FIG. 4 is a diagram showing the results of Example 4-1. FIG. 4 is a diagram showing the results of Example 4-1. FIG. 4 is a diagram showing the results of Example 4-2. FIG. 4 is a diagram showing the results of Example 4-2. FIG. 4 is a diagram showing the results of Example 4-3. FIG. 4 is a diagram showing the results of Example 4-3. FIG. 4 is a diagram showing the results of Example 4-4. FIG. 4 is a diagram showing the results of Example 4-4. 1 is a diagram specifically showing embodiments of aspects 1 and 2 of the present invention. FIG.

The present invention will be explained in detail below.
In addition, in this specification, a "(meth)acryloyl group" means a "methacryloyl group" or an "acryloyl group."

The present invention is a composition containing a resin component (A) having a host group and a polymer (B).
Furthermore, this polymer (B) was produced by reacting the resin component (A) in a solution.

When the resin component (A) having a host group further has a guest group, interaction occurs between the host group and the guest group, and this forms a structure similar to a crosslinked chain. However, since this interaction is not a covalent bond, separation and recombination can occur relatively easily. Further, in the case of a polymer having only a host group, it has a structure in which the main chain of the resin passes through the host group. The main chain of such a polymer can slide through the host group space.
Therefore, resin components with or without guest groups can have properties such as stimulus responsiveness, self-healing properties, and toughness.

When a polymerization reaction is carried out in a solution of a resin component (A) having a host group having such properties, the resulting polymer is formed in a state in which it is entangled in the crosslinked structure of the resin component (A). It is assumed that. As a result of the polymerization reaction proceeding with the pre-polymerization monomer of the polymer (B) penetrating into the resin component (A), a network structure of mutually penetrating non-crosslinked dissimilar polymers is formed, which improves the physical properties. It is presumed that this will have an impact on the environment and make it tougher.

In such a resin composition, if it has a structure that causes hydrogen bonding, it can have further excellent properties in terms of stimulus response, self-healing property, toughness, and the like. That is, hydrogen bonds form a structure similar to a crosslinked chain and cause dissociation and recombination of hydrogen bonds, which is presumed to contribute to improving these properties.
For example, by using a resin component (A) or a polymer (B) having a hydroxyl group or a carboxyl group, it is possible to obtain such an effect due to hydrogen bonding.

The resin composition of the present invention may further contain modified cellulose (C). This can further improve toughness. It is presumed that hydrogen bonding occurs between the resin component (A) and the modified cellulose (C), thereby providing suitable toughness.
Each of these components will be explained in detail below.

(Resin component (A))
The resin component (A) used in the present invention has a host group. Such compounds may have a host group and a guest group (A-1), or may have only a host group (A-2).

In the case of (A-1) having a host group and a guest group, a crosslinked structure is formed by the interaction between the host group and the guest group.
Such a resin may be a resin having both a host group and a guest group, or a mixture of a resin having a host group and a resin having a guest group. Known resin compositions can be used as such resin compositions.

In the case of having only host groups (A-2), the main chain of the resin component (A) penetrates at least a portion of the host groups.
Hereinafter, the host group and the guest group will be explained in detail, and then the resin having these will be explained in detail.

(host group)
In the resin component (A), the host group has the following general formula

(In the formula, R is the same or different and is hydrogen, an acetyl group, or an alkyl group having 50 or less carbon atoms, and X=5 to 7)
This is the structure represented by .

The above structure is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin derivative. The above-mentioned cyclodextrin is known as α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, etc., but any of these may be used, or two or more of these may be used in combination. good.

Of the R in the above general formula, both a hydrophilic host group in which 70% or more of R=H and a hydrophobic host group in which hydroxyl groups are less than 70% can be used, and when each of these is used, By combining with other materials suitable for each, the effects of the present invention can be obtained.

When a hydrophilic host group in which 70% or more of R═H is used as a host group, interaction can be caused by hydrogen bonding between the hydroxyl groups and the hydroxyl groups present in the host group. Therefore, it is preferable in that a strong resin composition can be obtained.

In the hydrophilic host group, R is more preferably 75% or more hydrogen, most preferably 90% or more hydrogen. Note that all of R may be hydroxyl groups.

When a hydrophobic host group containing less than 70% of hydroxyl groups is used, solubility in organic solvents can be obtained, so that it can be used uniformly with concomitant components such as resin component (B), modified cellulose (C), and other components. It becomes easy to mix. Therefore, it is preferable that any composition can be used as the resin component (B), and furthermore, it can be mixed with the modified cellulose (C) with high uniformity.

The cyclodextrin represented by the above general formula (1) may be one in which some or all of the hydroxyl groups in the proportions described above are substituted with R groups.
R in the general formula (1) can be at least one group selected from the group consisting of an acetyl group, an alkyl group having 50 or less carbon atoms, and -CONHR (R is a methyl group or an ethyl group). Such substitutions can be made by known methods.

When the resin component (A) is one having a host group and a guest group (A-1), it may be a polymer having both a host group and a guest group, or a polymer having a host group and a guest group. It may also be a mixture of polymers having groups. In any of these cases, the resin component (A) is obtained using a monomer having a host group and a monomer having a guest group as its raw material. A monomer having a host group and a monomer having a guest group, which can be used as raw materials for such resin component (A), will be explained in detail, and then a polymer using these will be explained in detail. .

(Monomer with host group)
The type of host group-containing polymerizable monomer is not particularly limited, as long as it has a host group and a functional group exhibiting polymerizability. Specific examples of functional groups exhibiting polymerizability include alkenyl groups, vinyl groups, etc., as well as -OH, -SH, -NH ₂ , -COOH, -SO ₃ H, -PO ₄ H, isocyanate groups, and epoxy groups ( glycidyl group), etc. These polymerizable functional groups can be introduced into the cyclodextrin or cyclodextrin derivative by substituting the hydrogen atom of one or more hydroxyl groups of the cyclodextrin. As a result, a host group-containing polymerizable monomer having a functional group exhibiting polymerizability is formed.

Examples of host group-containing polymerizable monomers include compounds in which a host group is bonded (for example, covalently bonded) to a vinyl compound having a radically polymerizable functional group. Examples of the functional group having radical polymerizability include groups containing a carbon-carbon double bond, and specifically, acryloyl group (CH ₂ =CH(CO)-), methacryloyl group (CH ₂ =CCH ₃ (CO)-), styryl group, vinyl group, allyl group, etc. These carbon-carbon double bond-containing groups may further have a substituent as long as radical polymerizability is not inhibited.

Specific examples of the host group-containing polymerizable monomer include vinyl-based polymerizable monomers to which the above host group is bonded. For example, the host group-containing vinyl monomer has the following general formula (h1)

(In formula (h1), Ra represents a hydrogen atom or a methyl group, R ^H represents the above-mentioned host group, and R ¹ represents a hydroxyl group, a thiol group, or an alkoxy group which may have one or more substituents. , a thioalkoxy group which may have one or more substituents, an alkyl group which may have one or more substituents, an amino group which may have one substituent, 1 Represents a divalent group formed by removing one hydrogen atom from a monovalent group selected from the group consisting of an amide group, an aldehyde group, and a carboxyl group, which may have 5 substituents. .)
Compounds represented by the following can be mentioned.

Alternatively, the host group-containing polymerizable monomer has the following general formula (h2)
(In formula (h2), Ra, R ^H and R ¹ have the same meanings as Ra, R ^H and R ¹ in formula (h1), respectively.)
Compounds represented by the following can be mentioned.

Furthermore, the host group-containing polymerizable monomer has the following general formula (h3)

(In formula (h3), Ra, R ^H and R ¹ have the same meanings as Ra, R ^H and R ¹ in formula (h1), respectively. n is 1 to 20, preferably 1 to 10, more preferably 1 to is an integer of 5. Rb represents hydrogen or an alkyl group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms).

In addition, the host group R ^H in the host group-containing polymerizable monomers represented by formulas (h1), (h2), and (h3) is a monovalent group obtained by removing one hydroxyl group from a cyclodextrin derivative. This is an example of a certain case.

The host group-containing polymerizable monomer has the following general formula (h4)
(In the formula, R ¹ is
(a) General formula (2) below
-R ³ -NH-R ⁴ (2)
(R ³ is an alkylene group having 3 to 20 carbon atoms, which may be linear or branched, and may have a substituent.
R ⁴ represents a (meth)acryloyl group or a vinyl group-containing alkyl group having 3 to 50 carbon atoms. ),
(a) General formula (3) below
-R ⁵ -NHCONH-R ⁶ (3)
(R ⁵ is an alkylene group having 3 to 20 carbon atoms, which may be linear or branched, and may have a substituent.
R ⁶ represents a (meth)acryloyloxyalkyl group having 4 to 50 carbon atoms or a vinyl group-containing alkyl group having 3 to 50 carbon atoms. )
or (c) the following general formula (4)
-R ⁵ -OCONH-R ⁶ (4)
( ^R5 and ^R6 are the same as above.)
represents one of the following.
R ² represents a hydrogen atom, an acyl group having 2 to 50 carbon atoms, or an alkyl group having 1 to 30 carbon atoms.
R ^H can include the above-mentioned host groups.

-CONHR ⁸ is preferably a methyl carbamate group or an ethyl carbamate group. -CONHR ⁸ is an ethyl carbamate group from the viewpoint that the cyclodextrin derivative is easily dissolved in other polymerizable monomers used together, and the polymer made of the cyclodextrin derivative is easy to form host-guest interaction. It is preferable that

In the above cyclodextrin derivative (h4), as shown in the above general formula (1), R ¹ and R ^H having the above polymerizable unsaturated group are connected via a nitrogen atom derived from an amino group. .

In the above general formula (1), one of R ¹ is
(a) General formula (2) below
-R ³ -NH-R ⁴ (2)
(R ³ is an alkylene group having 3 to 20 carbon atoms, which may be linear or branched, and may have a substituent.
R ⁴ represents a (meth)acryloyl group or a vinyl group-containing alkyl group having 3 to 50 carbon atoms. )
It is expressed as
The cyclodextrin derivative (h4) having the structure represented by the general formula (2) has a structure derived from a diaminoalkyl compound, R ² -NR ³ -NH-.

In the present invention, the diaminoalkyl compound used for producing the cyclodextrin derivative is unfavorable in terms of toxicity if the number of carbon atoms in the alkyl group is too small. Furthermore, if the distance between the main chain of the cyclodextrin derivative of the present invention and the cyclodextrin during polymerization is too short, the degree of freedom of the molecule including steric hindrance will decrease, which is not preferable in terms of functional expression. On the other hand, if the number of carbon atoms is too large, the distance between the main chain and the cyclodextrin during polymerization may become too large when considering synthesis (especially purification processes such as reprecipitation and recrystallization) and raw material procurement. This is not preferable due to concerns about functional expression and physical property deterioration. From the above, the carbon number R ³ of the diaminoalkyl group is preferably 3 to 20. More preferably 3 to 10, still more preferably 3 to 5.

The above R ⁴ is a functional group exhibiting radical polymerizability, and examples include an acryloyl group (CH ₂ =CH(CO)-) or a methacryloyl group (CH ₂ =CCH ₃ (CO)-). In this case, these carbon-carbon double bond-containing groups may further have a substituent as long as radical polymerizability is not inhibited.
Further, R ⁴ may be a vinyl group-containing alkyl group having 3 to 50 carbon atoms.

In addition, in the above general formula (1), R1 represents (a) the following general formula (3)
-R ⁵ -NHCONH-R ⁶ (3)
(R ⁵ is an alkylene group having 2 to 20 carbon atoms, which may be linear or branched, and may have a substituent.
R ⁶ represents a (meth)acryloyloxyalkyl group having 4 to 50 carbon atoms or a vinyl group-containing alkyl group having 3 to 50 carbon atoms. ).

As shown in the above general formula (3), the cyclodextrin derivative has a functional group that exhibits radical polymerizability via a urea bond, and has a (meth)acryloyloxyalkyl group or a vinyl group-containing alkyl group. It has a structure that has

The number of carbon atoms in the alkyl group of the (meth)acryloyloxyalkyl group is preferably 1 to 10, and specific examples include structures derived from isocyanates such as 2-methacryloyloxyethyl isocyanate and 2-acryloyloxyethyl isocyanate.

The number of carbon atoms R ⁵ in the diaminoalkyl group is preferably 3 to 20 for the same reason as R ³ above. More preferably, it is 3-10.

In addition, in the above general formula (1), R ¹ represents (c) the following general formula (4)
-R ⁵ -OCONH-R ⁶ (4)
(R ⁵ and R ⁶ are the same as above).

As shown in the above general formula (4), the cyclodextrin derivative has a functional group exhibiting radical polymerizability via a urethane bond, and has a (meth)acryloyloxyalkyl group or a vinyl group-containing alkyl group. It has a structure that has

The compounds represented by (h1) to (h4) mentioned above are, for example, the known compounds disclosed in Patent Documents 1 to 4 mentioned above. Therefore, it can be manufactured by referring to these documents.

In addition, the host group-containing polymerizable monomer can be one of the compounds represented by formula (h1), formula (h2), formula (h3), and formula (h4), or two types of compounds can be used alone. It can contain more than one species. In this case, Ra in formula (h1), formula (h2), and formula (h3) may be the same or different from each other. Similarly, R ^H in formula (h1), formula (h2), formula (h3), and formula (h4), and R ¹ in formula (h1), formula (h2), and formula (h3) are each the same or different from each other. There are cases.
The substituents defined in formulas (h1) to (h4) are not particularly limited. For example, substituents include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a halogen atom, a carboxyl group, a carbonyl group, a sulfonyl group, a sulfone group, and a cyano group. Examples include groups.

In (h1) to (h3), if R ¹ is a divalent group formed by removing one hydrogen atom from an amino group which may have one substituent, then the amino group The nitrogen atom of can be bonded to the carbon atom of the C═C double bond.

In (h1) to (h3), if R ¹ is a divalent group formed by removing one hydrogen atom from an amide group which may have one substituent, then the amide group carbon atoms can be bonded to the carbon atoms of the C═C double bond.

In (h1) to (h3), if R ¹ is a divalent group formed by removing one hydrogen atom from an aldehyde group, the carbon atom of the aldehyde group is the carbon of the C=C double bond. Can combine with atoms.

In (h1) to (h3), when R ¹ is a divalent group formed by removing one hydrogen atom from a carboxyl group, the carbon atom of the carboxyl group is the carbon of the C=C double bond. Can combine with atoms.

The host group-containing polymerizable monomers represented by (h1) to (h3) are, for example, (meth)acrylic acid ester derivatives (i.e., R ¹ is -COO-), (meth)acrylamide derivatives (i.e., R It is preferable that ¹ is -CONH- or -CONR-, and R has the same meaning as the above substituent. In this case, the polymerization reaction can proceed more easily, and the toughness and strength of the resulting polymer material can also be higher. Note that (meth)acrylic in this specification refers to either acrylic or methacryl.

R in the above -CONR- is, for example, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 6 carbon atoms. Specific examples of the host group-containing polymerizable monomer represented by formula (h1) include (h1-1) below.

In formula (h1-1), at least one X is a hydrogen atom, and n is 5, 6 or 7.

Specific examples of the host group-containing polymerizable monomer represented by formula (h2) include the following (h2-1) to (h2-9).

Compounds represented by formulas (h2-1), (h2-2), and (h2-3) have formulas (h2) in which R1 is -CONR- (R=methyl group), and α-cyclo It has a host group obtained by removing one hydroxyl group from a dextrin derivative, β-cyclodextrin derivative, or γ-cyclodextrin derivative.

Compounds represented by formulas (h2-4), (h2-5) and (h2-6) have formulas (h2) in which R1 is -CONH-, and are α-cyclodextrin derivatives and β-cyclodextrin derivatives, respectively. Dextrin derivatives and γ-cyclodextrin derivatives have a host group with one hydroxyl group removed.

Compounds represented by formulas (h2-7), (h2-8) and (h2-9) have formulas (h2) in which R1 is -COO-, and are α-cyclodextrin derivatives and β-cyclodextrin derivatives, respectively. Dextrin derivatives and γ-cyclodextrin derivatives have a host group with one hydroxyl group removed.

Specific examples of the host group-containing polymerizable monomer represented by formula (h3) include the following (h3-1) to (h3-3).

Compounds represented by formulas (h3-1), (h3-2) and (h3-3) have formula (h3) in which R1 is -COO-, n=2 and Rb are hydrogen atoms, and It has a host group with one hydroxyl group removed from α-cyclodextrin derivatives, β-cyclodextrin derivatives, and γ-cyclodextrin derivatives. Furthermore, in each of the cyclodextrin derivatives, the hydrogen atoms of the N-1 hydroxyl groups are substituted with acetyl groups (Ac). The host group-containing polymerizable monomers represented by (h1-1), (h2-1) to (h2-9) and (h3-1) to (h3-3) above are all acrylic. The effects of the present invention are not inhibited even in the case of a structure in which hydrogen at the meta position is replaced with a methyl group, that is, a methacrylic type.

The polymer compound having a host group includes a monomer unit based on the host group-containing polymerizable monomer and a monomer unit based on other radically polymerizable monomers described in detail below.

(guest group)
The resin component (A) in the resin composition of the present invention may have a guest group. Having a guest group is preferable in that a crosslinked structure due to host/guest interaction can be obtained.
The type of guest group is not limited as long as it is a group capable of host-guest interaction with the above-mentioned host group, and a wide range of known guest groups can be exemplified.

Examples of the guest group include linear or branched hydrocarbon groups having 3 to 30 carbon atoms, cycloalkyl groups, aryl groups, heteroaryl groups, and organometallic complexes, which have one or more substituents. You can leave it there. More specific guest groups include chain or cyclic alkyl groups having 4 to 18 carbon atoms. The chain alkyl group having 4 to 18 carbon atoms may be either straight chain or branched. The cyclic alkyl group may have a cage structure. The substituent is the same as the above-mentioned substituent, and includes, for example, a halogen atom (e.g., fluorine, chlorine, bromine, etc.), a hydroxyl group, a carboxyl group, an ester group, an amide group, an optionally protected hydroxyl group, etc. be able to.

Other guest groups include, for example, alcohol derivatives; aryl compounds; carboxylic acid derivatives; amino derivatives; azobenzene derivatives having a cyclic alkyl group or phenyl group; cinnamic acid derivatives; aromatic compounds and their alcohol derivatives; amine derivatives; ferrocene derivatives; azobenzene; naphthalene derivative; anthracene derivative; pyrene derivative; perylene derivative; clusters composed of carbon atoms such as fullerene; A monovalent group formed by removing an atom) can also be mentioned.

Further specific examples of the guest group include t-butyl group, n-octyl group, n-dodecyl group, isobornyl group, adamantyl group, and groups to which the above substituents are bonded.

(Monomer with guest group)
Specific examples of the guest group-containing polymerizable monomer include vinyl-based polymerizable monomers to which the above-mentioned guest groups are bonded (for example, covalently bonded).

For example, the guest group-containing polymerizable monomer has the following general formula (g1)

(In formula (g1), Ra represents a hydrogen atom or a methyl group, R ^G represents the above guest group, and R ² has the same meaning as R ¹ in formula (h1).)
Polymerizable monomers represented by:

Among the polymerizable monomers represented by formula (g1), (meth)acrylic esters or derivatives thereof (i.e., R ² is -COO-), (meth)acrylamide or derivatives thereof (i.e., R ¹ is - CONH- or -CONR-, where R has the same meaning as the above substituent). In this case, the polymerization reaction can proceed more easily, and the toughness and strength of the resulting polymer material can also be higher.

Specific examples of guest group-containing polymerizable monomers include n-hexyl (meth)acrylate, n-octyl (meth)acrylate, n-dodecyl (meth)acrylate, adamantyl (meth)acrylate, and (meth)acrylate. ) Hydroxyadamantyl acrylate, 1-(meth)acrylamidoadamantane, 2-ethyl-2-adamantyl(meth)acrylate, N-dodecyl(meth)acrylamide, t-butyl(meth)acrylate, 1-acrylamidoadamantane, N- (1-adamantyl) (meth)acrylamide, N-benzyl (meth)acrylamide, N-1-naphthylmethyl (meth)acrylamide, ethoxylated o-phenylphenol acrylate, phenoxypolyethylene glycol acrylate, isostearyl acrylate, nonylphenol EO adduct Examples include acrylate, isobornyl (meth)acrylate, and the like.

The guest group-containing polymerizable monomer can be produced by a known method. Moreover, a commercially available product can also be used as the guest group-containing polymerizable monomer.

(Other radically polymerizable monomers)
Other radically polymerizable monomers do not fall under the above-mentioned host group-containing polymerizable monomers and guest group-containing monomers, and are the above-mentioned host group-containing polymerizable monomers and guest group-containing polymerizable monomers described below. Examples include various compounds that can be copolymerized with. Examples of the other radically polymerizable monomers include various known vinyl polymerizable monomers.

As a specific example of the vinyl polymerizable monomer, the following general formula (a1) is used.

(In formula (a1), Ra is a hydrogen atom or a methyl group, R3 is a halogen atom, a hydroxyl group, a thiol group, an amino group that may have one substituent or a salt thereof, and one substituent. carboxyl group or a salt thereof which may have one or more substituents, an amide group or a salt thereof which may have one or more substituents, a phenyl group which may have one or more substituents)
Compounds represented by the following can be mentioned.

In formula (a1), when R ³ is a carboxyl group having one substituent, the hydrogen atom of the carboxyl group is a hydrocarbon group, a hydroxyalkyl group (for example, a hydroxymethyl group, a 1-hydroxyethyl group, a 2- hydroxyethyl group), methoxypolyethylene glycol (the number of ethylene glycol units is 1 to 20, preferably 1 to 10, particularly preferably 2 to 5), ethoxypolyethylene glycol (the number of ethylene glycol units is 1 to 20, preferably 2 to 5), Examples include carboxyl groups (ie, esters) substituted with groups 1 to 10, particularly preferably 2 to 5).
In formula (a1), when R ³ is an amide group having one or more substituents, that is, a secondary amide or a tertiary amide, one hydrogen atom or two hydrogen atoms of the primary amide Examples include amide groups in which atoms are independently substituted with hydrocarbon groups or hydroxyalkyl groups (eg, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl).

Among them, in formula (a1), R ³ is a carboxyl group in which a hydrogen atom is substituted with an alkyl group having 1 to 10 carbon atoms, or an amide in which one or more hydrogen atoms are substituted with an alkyl group having 1 to 10 carbon atoms. It is preferable that it is a group. In this case, the other radically polymerizable monomers have relatively high hydrophobicity, and copolymerization with the host group polymerizable monomer easily proceeds. More preferably, the alkyl group as a substituent has 2 to 8 carbon atoms, particularly preferably 2 to 6 carbon atoms, and in this case, the toughness and strength of the resulting polymer material are likely to be improved. This alkyl group may be either straight chain or branched.

Specific examples of the monomer represented by formula (a1) include (meth)acrylic acid, allylamine, maleic anhydride, methyl (meth)acrylate, ethyl (meth)acrylate, and n-(meth)acrylate. Propyl, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, N,N -Dimethyl (meth)acrylamide, N,N-diethylacrylamide, N-isopropyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylamide, 2 -hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ethoxy-diethylene glycol acrylate, methoxy-triethylene glycol acrylate, methoxy-polyethylene glycol acrylate, styrene and the like. These can be used alone or in combination of two or more.

The monomer represented by formula (a1) is preferably a hydrogen bond donating monomer. A hydrogen bond-donating monomer means a monomer containing hydrogen-bonding hydrogen. More specifically, it refers to a monomer having in its molecule a functional group containing hydrogen that forms a hydrogen bond, such as a hydroxyl group, a carboxyl group, an amino group, or the like.

The hydrogen bond-donating monomer is particularly preferably a hydroxyl group-containing monomer and/or a carboxyl group-containing monomer, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ( Particularly preferred is meth)acrylic acid. In the case of the hydroxyl group-containing monomer, it is preferable to have a secondary hydroxyl group in that it is not too strong and has an appropriate hydrogen bond compared to a primary hydroxyl group. Examples of such monomers include 2-hydroxypropyl (meth)acrylate and 2-hydroxybutyl (meth)acrylate.

Furthermore, a monomer having an ether group may be used. Since such monomers can also form hydrogen bonds, the same effects as the above-mentioned hydroxyl group-containing monomers can be obtained. Examples of monomers having such an ether group include vinyl alkyl ether compounds, alkyl ether compounds of hydroxyalkyl (meth)acrylic acid, and the like. Note that when such a monomer having an ether group is used, it is preferable that the resin composition as a whole has a hydrogen bond-donating functional group in any of the components (A) to (C). The ether group is for hydrogen bond acceptance.

In the resin component (A), the content of the host group-containing polymerizable monomer unit is not particularly limited. For example, the resin component (A) may contain 0.01 to 10 mol% of host group-containing polymerizable monomer units based on the total number of moles of monomer units constituting the resin component (A). In this case, host-guest interaction is likely to occur in the polymeric material, and mechanical strength is likely to be improved. The host group-containing polymerizable monomer unit preferably contains 0.05 mol% or more, and preferably 0.1 mol% or more, based on the total number of moles of monomer units constituting the resin component (A). is more preferable, it is even more preferable to contain 0.5 mol% or more, and it is particularly preferable to contain 1 mol% or more. Further, the host group-containing polymerizable monomer unit preferably contains 8 mol% or less, more preferably 6 mol% or less, based on the total number of moles of monomer units constituting the resin component (A). It is preferably contained in an amount of 5 mol% or less, more preferably 4 mol% or less.

In the resin component (A), the content of the guest group-containing polymerizable monomer unit is not particularly limited. For example, the guest group-containing polymerizable monomer unit can be contained in an amount of 0 to 10 mol % based on the total number of moles of monomer units constituting the resin component (A). In this case, host-guest interaction is likely to occur in the polymeric material, and mechanical strength is likely to be improved. The guest group-containing polymerizable monomer unit preferably contains 0.05 mol% or more, and 0.1 mol% or more, based on the total number of moles of the monomer units constituting the polymer compound having a guest group. It is more preferable to contain it, more preferably to contain it in an amount of 0.5 mol% or more, and especially preferably to contain it in an amount of 1 mol% or more. In addition, the guest group-containing polymerizable monomer unit preferably contains 8 mol% or less, more preferably 6 mol% or less, based on the total number of moles of monomer units constituting the resin component (A). It is preferably contained in an amount of 5 mol% or less, more preferably 4 mol% or less.

The resin component (A) mentioned above can be obtained by any known polymerization method. Specifically, solution polymerization in an organic solvent can be mentioned. A thermal polymerization reaction using a radical polymerization initiator, a photopolymerization reaction using a photopolymerization initiator, etc. can be used.

(Polymer (B))
As described above, the polymer (B) is obtained by carrying out a polymerization reaction in the presence of the resin component (A). By containing the polymer (B) obtained by such a method, the toughness is higher than when the polymer obtained by a general method is simply mixed with the resin component (A). It is preferable because it has excellent properties.

As described above, in the resin composition of the present disclosure, each component is preferably selected so as to cause hydrogen bonding. For example, when the host group has a dextrin structure having a large number of hydroxyl groups, a monomer having a functional group that forms a hydrogen bond with the hydroxyl groups in the polymer (B) may be used. can.　

Specific examples of such monomers include the above-mentioned hydroxyl group-containing monomers, ether group-containing monomers, etc. Specifically, for example, 2-methoxyethyl (meth)acrylate, Examples include 2-ethoxyethyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, and 4-ethoxybutyl (meth)acrylate. The monomers are not limited to these monomers as long as they are polar monomers that dissolve with the resin component (A) and have moderate compatibility so as not to cause partial separation or crystallization even after polymerization. Two or more of these may be used in combination.

(Polymerization of polymer (B))
The polymer (B) reacts in the presence of the resin component (A). It is presumed that by manufacturing in this way, the polymer (B) is formed so as to be entangled with the resin component (A) having a crosslinked structure, resulting in high interaction, which improves the performance of the resin. Ru.

In the polymerization of the polymer (B), the resin component (A) may be dissolved in a solvent and reacted as a solution, or the resin component (A) may be reacted as a solution without using a solvent. The resin component (A) may be dissolved or swollen in the monomer and then reacted. As detailed below, when the polymerization reaction of polymer (B) is carried out in the presence of modified cellulose (C), it is difficult to dissolve all of the components, so some or The reaction may be carried out in a state where all the components are swollen. As described above, the effects of the present invention can be obtained by polymerizing the polymer (B) in the presence of the resin component (A).

When carrying out the reaction in a resin solution, the solvent is not particularly limited as long as it dissolves the monomers that are the raw materials for the resin component (A) and the polymer (B), but examples include dimethyl sulfoxide, Examples include N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and pyridine.

In the resin solution, the amount of resin component (A) in the polymerization of polymer (B) is preferably 10 to 50% by weight based on the total amount of resin component (A) and solvent.

The polymer (B) is preferably obtained by polymerization of unsaturated bonds. The monomers constituting such a polymer are not particularly limited, and may include various acrylic monomers, vinyl monomers, and the like. More specifically, the compounds exemplified as monomers that can be used for the above-mentioned "other radically polymerizable monomers" can be mentioned.

When carrying out the polymerization reaction of the polymer (B) in a resin solution, it is particularly preferable that the above-mentioned resin component (A) is a component that can be uniformly dissolved in the resin solution. By using such a material, the obtained polymer will have a polymer present in the resin chain having a three-dimensional structure of the resin component (A), so that the effects of the present invention can be favorably obtained. can.

(Cellulose (C) modified with a compound having at least one functional group selected from the group consisting of carboxyl group, hydroxyl group, amino group and amide group)
The resin composition of the present invention comprises cellulose (C) (hereinafter simply referred to as modified cellulose) modified with a compound having at least one functional group F selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, and an amide group. It may contain C).

Modified cellulose (C) is obtained by esterifying some of the hydroxyl groups of the cellulose molecule with a compound having at least one functional group selected from the group consisting of a carboxy group, a hydroxyl group, an amino group, and an amide group. Since these functional groups cause hydrogen bonds, they cause hydrogen bonds to occur between the resin component (A) and the polymer (B), thereby improving physical properties.

The shape of the modified cellulose (C) is not particularly limited, but the shape of the modified cellulose (C) is not particularly limited. It is possible to suitably use those whose surface has been modified with a compound having the above-mentioned properties.

Micronized cellulose fibers are wood fibers (pulp) that have been refined down to the nano-order, and have received particular attention in recent years as a naturally-derived material. The use of micronized cellulose fiber as a filler is being considered, and it is known that strength is improved when blended into a resin, and many studies have been made from this perspective.

The particle size of the micronized cellulose fibers is not particularly limited, but preferably has an average particle size of 1 to 30 μm as measured by nano-X-ray CT, for example. Such micronized cellulose fibers may be so-called cellulose nanofibers, which are micronized to the nano-order.

Also in the resin composition of the present invention, suitable toughness can be obtained by using such modified cellulose (C). Furthermore, micronized cellulose fibers surface-modified with such specific functional groups can be dissolved or dispersed in an ionic liquid or the like. In this way, after being dissolved or dispersed in a liquid medium, it may be composited by the method detailed below, and then precipitated.

Cellulose in which at least a portion of the hydroxyl groups are esterified is particularly preferred since it has a high affinity with the resin component (A) and the polymer (B) and can be mixed uniformly. Furthermore, hydrogen bonds can occur with each component in the composition. This makes it possible to improve the physical properties of the resin composition.

The micronized cellulose fibers may include at least one of cellulose and cellulose derivatives. Among these, the cellulose material is preferably a cellulose derivative from the viewpoint that hydrogen bonding with the resin component (A) is likely to occur.

The above-mentioned cellulose derivative is, for example, a compound in which cellulose is modified with another functional group, and can also be referred to as a so-called modified cellulose. Specifically, the cellulose derivative has a structure in which a hydroxyl group in a structural unit constituting cellulose or a hydrogen atom of the hydroxyl group is substituted with another functional group. Preferably, the cellulose has a structure in which a hydroxyl group in a structural unit constituting the cellulose is substituted with another functional group.

The cellulose derivative described above is preferably cellulose modified with a compound having at least one functional group F selected from the group consisting of a carboxy group, a hydroxyl group, an amino group, and an amide group. In other words, the above-mentioned cellulose derivative has a structure in which the hydroxyl group in the structural unit (glucose unit) constituting cellulose is substituted with at least one functional group selected from the group consisting of a carboxy group, a hydroxyl group, an amino group, and an amide group. It is preferable to have. In this case, since hydrogen bonding with the polymer A is likely to occur in the cellulose material, the polymer composite material can have excellent flexibility, toughness, and hardness.

Among these, in the cellulose derivative, at least one functional group selected from the group consisting of a carboxy group, a hydroxyl group, an amino group, and an amide group is preferably one selected from the group consisting of a carboxy group and a hydroxyl group.

The cellulose derivative can be obtained, for example, by modifying cellulose with a compound having the above functional group (for example, functional group F). Here, the compound having the above functional group is referred to as "compound F."

Examples of the compound having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, and an amide group include a compound having a carboxy group, a compound having a hydroxyl group, a compound having an amino group, and a compound having an amide group. These include, for example, a wide variety of known compounds.

Specifically, examples of compound F include citric acid, succinic acid, malic acid, phthalic acid, isophthalic acid, terephthalic acid, trimesic acid, oxalic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, malonic acid, etc. be able to. Among these, compound F is preferably citric acid, from the viewpoints of easy production of the cellulose derivative and easy hydrogen bonding with polymer A.

Therefore, the cellulose derivative is preferably citric acid-modified cellulose.

In the cellulose derivative, the amount of the functional group derived from the compound F introduced is, for example, 0.1 to 5 mmol/g, preferably 0.5 to 3 mmol/g, and more preferably 1 to 2 mmol/g.

A specific method for producing a cellulose derivative includes, for example, a method in which cellulose and the above compound F are reacted. The reaction method between cellulose and the above-mentioned compound F is not particularly limited, and for example, a wide variety of known condensation reactions, addition reactions, etc. can be employed.

The reaction between cellulose and the above compound F can be carried out, for example, in the presence of a catalyst. The type of catalyst is not particularly limited, and examples include acids, alkalis, and the like. The catalyst is preferably an alkali, and specific examples include alkali metal hydroxides such as sodium hydroxide, ammonia, and organic amines.

The reaction temperature between cellulose and the above compound F is also not particularly limited, and can be appropriately selected depending on the reactivity and the like. For example, the reaction between cellulose and the above compound F can be carried out at a temperature of 20 to 200°C, preferably 50 to 150°C. The reaction time is also not particularly limited, and can be set to an appropriate time depending on the reaction temperature, for example, from 30 minutes to 20 hours.

The reaction between cellulose and the above compound F can be carried out in various solvents or without solvent.

The molecular weight of the cellulose or cellulose derivative contained in the cellulose material is also not particularly limited. For example, the weight average molecular weight of cellulose or a cellulose derivative is 5,000 to 1,000,000, preferably 10,000 to 900,000, more preferably 100,000 to 800,000.

Furthermore, it is preferable that the above-mentioned modified cellulose (C) is blended simultaneously with the polymerization of the above-mentioned polymer (B). By simultaneously blending them in such a polymerization step, they can be uniformly mixed with the resin component (A) and the polymer (B). Furthermore, when surface-treated carbon nanofibers as described above are used, interactions such as hydrogen bonding occur before the polymer (B) is polymerized. Therefore, the obtained resin composition is particularly preferable in that the affinity between each component is high.

The modified cellulose (C) may be mixed into the raw material monomer in the polymerization of the resin component (A), and the resin component (A) may be polymerized in the presence of the modified cellulose (C).

(About preferred embodiments)
Although the present invention is as described above, among these, either of the following (Aspect 1) or (Aspect 2) is particularly preferable. A schematic diagram specifically showing these aspects 1 and 2 is shown in FIG. 14.

(Aspect 1)
Aspect 1 corresponds to Examples 1 to 3 below, in which the resin component (A) has both a host group and a guest group, and 70% or more of R in the host group is R=H. This is a certain kind of situation. In Embodiment 1, when the modified cellulose (C) is blended, it is preferable to polymerize the polymer (B) in a solution of the resin component (A). Furthermore, when blending the modified cellulose (C), it is preferably added at the same time as the monomer in the step of polymerizing the polymer (B) in the solution of the resin component (A).

In such embodiment 1, the interaction between the host group and the guest group functions as a reversible crosslink.

In the above embodiment 1, each of the above-mentioned components (A) to (C) is preferably contained in the following proportions (% by weight) with respect to the total weight of (A) to (C).
Resin component (A): 57-86%
Polymer (B): 9.2 to 38.2%
Modified cellulose (C): 4-6%

In particular, in order to suitably obtain the effects of the present invention, the mixing ratios of A=76.2, B=19.0, and C=4.8 are particularly important, and it is particularly preferable to satisfy these ratios.

(Aspect 2)
Embodiment 2 corresponds to Example 4 below, and is an embodiment in which the resin component (A) has only a host group, and less than 30% of R in the host group is R=H. . That is, the main chain of the resin component (A) and/or the polymer (B) penetrates the cyclodextrin ring that is the host group. A polymer having such a penetrating structure will slide when stress is applied, thereby producing excellent physical properties.

In this embodiment 2, when the modified cellulose (C) is further blended, it is preferably added to the monomers constituting the resin component (A) during polymerization of the resin component (A).

In such an embodiment, when polymerizing the polymer (B), the polymer (B) is polymerized in a composition called resin component (A) formed in the presence of the modified cellulose (C). That will happen. In this case, since it is difficult to form a solution that dissolves the monomers that are the raw materials for the polymer (B) and the above composition, the raw materials for the polymer (B) are added to the composition molded into the desired shape. Preferably, the monomer is impregnated and polymerized.

In the second embodiment, each of the components (A) to (C) described above is preferably contained in the following proportions (% by weight) based on the total weight of (A) to (C).
Resin component (A): 48-68%
Polymer (B): 30-50%
Modified cellulose (C): 1.5-3%

In particular, in order to suitably obtain the effects of the present invention, the blending ratios of A = 48.5%, B = 50%, and C = 1.5% are particularly important, and it is particularly preferable to satisfy these ratios.

(Method for manufacturing resin composition)
The resin composition of the present invention is obtained by polymerizing the polymer (B) in the presence of the resin component (A).

The polymerization method for the polymer (B) is not particularly limited, and can be carried out by a general method. Specifically, radical polymerization by heat, radical polymerization by light, anionic polymerization, cationic polymerization, etc. can be mentioned. Among these, radical polymerization is particularly preferred.

When performing the radical polymerization using light, it is preferable to use a photopolymerization initiator. The photopolymerization initiator is not particularly limited and includes, for example, 1-hydroxycyclohexylphenylketone (trade name: IRGACURE184), 2-hydroxy-2-methylpropiophenone (trade name: IRGACURE1173), 2-methyl-1- Acetophenones such as [4-(methylthio)phenyl]-2-morpholinopropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, etc. System initiator; benzoin system initiator such as benzoin, 2,2-dimethoxy-1,2-diphenylethan-1-one; benzophenone, [4-(methylphenylthio)phenyl]phenylmethanone, 4-hydroxybenzophenone, Benzophenone initiators such as 4-phenylbenzophenone and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; Thioxanthone initiators such as 2-chlorothioxanthone and 2,4-diethylthioxanthone; Acylphosphine oxide initiators such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; 1,2-octanedione, 1-[4-(phenylthio) ) phenyl], 2-(0-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazoyl-3-yl]-, 1-(0-acetyloxime), etc. Ester-based initiators and the like can be used. The amount of the photopolymerization initiator used is preferably 0.1 to 2% by weight based on the total amount of monomers constituting the polymer (B).

Conditions for photopolymerization are not particularly limited, and examples of light sources include high-pressure mercury lamps, LED lamps, metal halide lamps, and the like.

When carrying out the radical polymerization reaction by the above-mentioned thermal reaction, it is preferable to use a radical polymerization initiator. The radical polymerization initiator is not particularly limited, and includes azobisisobutyronitrile (AIBN), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methylbutyronitrile), Dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, cumene hydroperoxide, etc. can be used.
The amount of the thermal polymerization initiator used is preferably 0.1 to 2% by weight based on the total amount of monomers constituting the polymer (B).

The blending amount of (A) and (B) is preferably such that (A)/((A)+(B)) (weight ratio) is 0.5 to 0.9. By setting the content within this range, it is preferable that the effect of the host-guest interaction in the resin component (A) can be sufficiently maintained while toughening can be achieved due to the network structure with the polymer B. The lower limit is preferably 0.5, more preferably 0.7. The upper limit is preferably 0.9, more preferably 0.85.

As described above, the physical properties of the resin composition of the present invention are improved when there are many hydrogen bonds. Therefore, in the above embodiment 2, by performing polymerization in the presence of component (C) during the polymerization process of resin component (A), component (C) is more uniformly dispersed in the composition. . Furthermore, the polymerization of polymer (B) is also carried out in the presence of component (C). As a result, the entire composition has high uniformity and can have better physical properties.

In order to obtain such a composition, the resin component (A) may be polymerized in the presence of the component (C). Since the above component (C) does not have high solubility in ordinary solvents or monomers that are raw materials for the resin component (A), it is dissolved or dispersed in an ionic liquid, and then the resin component (A) is dissolved or dispersed in an ionic liquid. It may also be mixed with a monomer serving as a raw material.

As mentioned above, as the modified cellulose (C), cellulose nanofibers surface-treated with citric acid can be suitably used. Since modified cellulose (C) is not a highly soluble component, it cannot be dissolved in the reaction solvent.

Therefore, it is preferable to use an ionic liquid in order to highly disperse the modified cellulose (C) in the liquid medium. By mixing the modified cellulose (C) with a liquid medium, it is dissolved or highly dispersed, and this is mixed with the raw material monomer of the resin component (A) in the solvent, and in this state, the resin component (A) is polymerized. It is preferable to do this.

In this case, after polymerizing the resin component (A), the ionic liquid is removed by washing, and then the monomer that will be the raw material for the polymer (B) is added to form the polymer (B). ) is preferably carried out. When performing such a method, the resin component (A) containing component (C) is often in a solid state. In this case, after polymerizing the resin component (A), it is molded into a desired shape such as a film shape, and the monomer constituting the polymer (B) is It may also be molded by impregnating it with a polymer (B) and causing a polymerization reaction of the polymer (B) by light irradiation, heating, etc.

(Molding method)
The resin composition of the present invention can be one that is molded into a predetermined shape by molding a composition containing a solvent by a method such as a casting method.

The present invention also provides a resin molded product made of the above-mentioned resin composition having an elastic modulus of 5 to 60 MPa. That is, it is preferable that a resin molded article using the resin composition of the present invention has such an excellent modulus of elasticity. The elastic modulus is more preferably 10 MPa or more, and even more preferably 15 MPa or more. The elastic modulus is more preferably 55 MPa or less.

The resin molded product of the present invention preferably has a toughness of 5 to 90 MJm ^-3 . It is preferable that a resin molded article using the resin composition of the present invention has the above-mentioned elastic modulus and also has excellent toughness. The toughness is more preferably 10 MJm ^-3 or more, and even more preferably 20 MJm ^-3 or more. The toughness is more preferably 70 MJm ^-3 or less, even more preferably 65 MJm -3 or less, and most preferably 60 MJm ^-3 or less.

The present invention will be specifically described below based on Examples. Note that the present invention is not limited to the following examples.

Each monomer used in the following examples means the following.
AdAAm: N-(1-adamantyl)acrylamide AA: Acrylic acid CAC: Citric acid modified cellulose (produced according to the method of JP 2021-707698, Example 1-1)
βCDAAmMe was synthesized according to the production method described in Macromolecules 2017, 50, 8, 3254-3261.
TAcγCDAAmMe was synthesized according to the production method described in Macromolecules 2019, 52, 7, 2659-2668. Macromolecules 2019, 52, 18, 6953-6962.

(Example 1)
In a centrifuge tube, add 2-hydroxypropyl acrylate (HPA), host monomer (βCDAAmMe), guest monomer (AdAAm), photoinitiator (IRGACURE184), and dimethyl sulfoxide (DMSO) as a solvent so that the monomer concentration is 20% by weight. In addition, ultraviolet light from a mercury lamp was irradiated for 135 minutes to obtain a primary polymer solution. Methoxyethyl acrylate (MEA) as a secondary monomer, CAC, and a photoinitiator were mixed into the obtained primary polymer solution using a planetary ball mill, and the mixture was transferred to a Teflon (registered trademark) beaker and photopolymerized. A film-like polymer was obtained by transferring to a petri dish and removing DMSO in a windy oven (80° C., 15 hours) and a vacuum oven (80° C., 1 day). To represent each component, the resulting composite material is designated as pHPA(100-xy)-βCDAAmMe(x)-AdAAm(y)/pMEA(z)/CAC(w). Here, x and y are the mol% of the host and guest molecules in the primary polymer, respectively, z is the weight% of the secondary polymer in the polymer, and w is the weight% of CAC to the polymer.

In addition, a primary polymer network containing reversible crosslinking is called SC (Single Crossnetwork), and a material in which a linear polymer (Penetrating polymer) is introduced into SC(x,y) is called SCP (Single Crossnetwork with Penetrating Polymer). er), compounding CAC The resulting material is expressed as SCP(x, y, z) / CAC(w). The material preparation scheme is shown in Figure 2, and the amounts of each reagent during primary polymer preparation and mixing using a planetary ball mill are summarized in Tables 1 and 2.

Tensile Test The obtained film was subjected to hot vacuum pressing at a temperature of 80° C. and a pressing force of 5 kN, and the thickness of the sample was adjusted to 0.4 to 0.6 mm. Thereafter, it was cut into a strip of 20 mm (vertical) x 5 mm (horizontal) and subjected to a tensile test (Shimadzu Autograph AG-X) at a tensile speed of 1 mm/s. Below, the stress-strain curves (FIGS. 3 a to c) and the relationship between Young's modulus and toughness (d to f) for each sample during stretching are shown. Young's modulus represents the hardness of a material and is calculated from the initial slope of the stress-strain curve. On the other hand, toughness refers to the toughness of a material and is determined from the area of the stress-strain curve. These generally have a trade-off relationship, and the higher the Young's modulus and the higher the toughness, the harder, stronger, and more durable the material becomes.

First, when comparing pHPA in which only HPA was polymerized and SC(1,1) in which reversible crosslinking was introduced, Young's modulus and toughness were significantly improved due to host-guest interaction using CD (a, d). Next, in SCP (1, 1, z) where pMEA, a linear polymer, is introduced into this SC (1, 1), in SCP (1, 1, 20) where the weight% of the secondary polymer is 20%, Improvement in toughness was confirmed (b, e). Furthermore, SCP (1, 1, 20)/CAC (5), in which 5 wt% of CAC was added to SCP (1, 1, 20), had a lower strain at break during stretching than a sample that did not contain CAC. It became larger and showed a larger Young's modulus while maintaining high toughness (c, f).

From the results of these Examples, it is clear that the resin composition of the present invention has excellent strength.

(Example of monomer production)
SH-01 is a compound represented by the above general formula.
The compound was synthesized as follows.
Weighed 31 g (26 mmol) of mono-6-(2-aminopropyl)amino-6-β-cyclodextrin and 3.7 g (37 mmol) of triethylamine into a 500 mL glass round-bottomed flask, and dissolved them in 74 g of dimethylformamide. I let it happen. To this solution, 5.1 g (33 mmol) of methacrylic anhydride was added dropwise over 20 minutes with stirring, and the mixture was further stirred for 90 minutes. Next, the reaction solution was poured into 340 g of acetone with vigorous stirring and left overnight. After the resulting precipitate was filtered off and washed with acetone, the resulting white solid was dissolved in 52 g of distilled water and treated with a column packed with anion exchange resin DOWEX 50-100 mesh (OH-form). Thereafter, the precipitated white solid was dissolved in 45 g of dimethylformamide, separated by filtration, and reprecipitated with 203 g of acetone. The precipitated white solid was filtered, washed with acetone, and dried under vacuum to obtain 1 g (0.778 mmol) of the desired β-cyclodextrin having a methacrylic group.
1H NMR: (DMSO-d6, 400 MHz): δ = 1.52-1.59 (m, 2H, methylene), 1.83 (s, 3H, Me), 2.53-2.58 (m, 2H, methylene), 3.11-3.15 (m , 2H, methylene), 3.24-3.74 (m, 42H, C(2, 3, 4, 5, 6)H of CD), 4.41-4.54 (m, 6H, primary OH), 4.78-4.90 (m, 7H , C(1)H of CD), 5.28 (br, 1H, vinyl), 5.61 (br, 1H, vinyl), 5.69- 5.79 (m, 14H, secondary OH), 7.93 (t, J = 5.2 Hz, 1H , -NHCO-).

(Example 2)
Exactly the same experiment was conducted using SH-01, a monomer produced according to the above synthesis example, instead of βCDAAmMe. The ratio of each monomer used in the polymer of Example 2 is as follows.
Each of the following polymers (1) to (5) was produced.
(1): Material consisting of HOP-A(N), SH-01 and AdAAm* SH-01: AdAAm = 1: 1 (mol)
(2): Material polymerized by mixing 20% by weight of MEA in the DMSO solution of (1)
*Primary polymer: MEA = 80:20 (weight%)
(3): A material obtained by mixing 30% by weight of MEA in the DMSO solution of (1) and polymerizing it. (4): A material in which 5% by weight of CAC was added during the preparation of (2).
* Polymer: CAC = 100:5 (weight%)
(5): Material to which 5% by weight of CAC was added during production of (3)

The composition ratio of each raw material during polymerization of the polymer (1) is shown in Table 3 below.
(*Monomer concentration: 20% by weight)

Using the polymer (1) thus obtained, each polymer/composition was further obtained according to the composition ratios (2) to (5) shown in Table 4 below.

The results of the same evaluation as in Example 1 are shown in FIG.
From FIG. 4, it became clear that the polymer of Example 2 also had good performance.

(Example 3)
Using the same method as in Example 2 above, the ratio of the polymer (1) (resin component (A)) and MEA (polymer B) was adjusted to (A)/(B) = 0/100, 50/50, Polymers each having a different concentration of 60/40, 70/30, 75/25, 80/20, 85/15, 90/10, and 100/0 were obtained.
The glass transition temperature of these samples was measured by differential scanning calorimetry.
The results are shown in Table 5 below.

In Table 5 above, in the resin composition targeted by the present invention, the glass transition temperatures of the resin component (A) and the polymer (B) are observed.
In the resin composition of the present invention, the glass transition temperature is higher than that of each polymer alone. These experimental results imply that the resin is more constrained by including the two components than if they were alone. Therefore, this result provides evidence that hydrogen bonding has occurred.

(Example 4)
(Polymerization of resin component (A) in the presence of citric acid-modified cellulose)
1 mol% TAcγCDAAmMe was dissolved in methyl acrylate (MA) and 20 mol% acrylic acid (AA), photopolymerization initiator IRGASURE184 was added, and ultrasonic waves were irradiated for 1 hour. A 7 wt% CAC solution was prepared by dissolving 3 wt% of CAC in the monomer solution with the ionic liquid 1-Butyl-3-methlimidazolium chloride (BMIm Cl) and heating and stirring at 100°C for one day. Photopolymerization was performed by mixing the monomer solution and CAC solution. Subsequently, the obtained material was immersed in a 10-fold weight solution of 2-propanol and washed for 3 days by changing the solution every day. Subsequently, the material was washed with water in the same manner as above to remove the ionic liquid, and then dried under heat under vacuum to obtain a CAC composite material SC/CAC. The blending ratio of each component is shown in Table 6 below.

(Polymerization of polymer (B))
SC/CAC was swollen with a monomer solution and photopolymerized. 2-Hydroxyethyl Acrylate (HEA), 2-Methoxyethyl Acrylate (MEA), and AA were used as monomers. The resulting material was evacuated overnight at 70°C to remove residual monomers, and an SCP/CAC composite material was produced. The monomers used as raw materials for the polymer (B) in this step are MEA (Table 6), HEA (Table 7), MEA+AA (Table 8), and HEA+AA (Table 9). The polymerization was carried out while changing the polymerization ratio.

In the above table, the weight ratios of SC/CAC:MEA are (a) 80:20, (b) 70:30, (c) 60:40, and (d) 50:50.

In the above table, the weight ratios of SC/CAC:HEA are (a) 80:20, (b) 70:30, (c) 60:40, (d) 50:50, and (e) 40:60. .

In the above table,
SC/CAC:pMEA-AA weight ratio is 50:50
The molar ratio of MEA: AA is (a) 80:20, (b) 50:50, (c) 20:80
It is.

SC/CAC:pHEA-AA weight ratio is 50:50
The molar ratio of HEA:AA is
(a) 80:20, (b) 50:50, (c) 20:80

A tensile test was conducted on the above polymer. The results are shown in Figures 5-12. From the results shown in the figure, it is clear that the physical properties of the resin composition are greatly improved by the polymer (B).

The resin composition of the present invention can be used as a molding material in various fields.

Claims (13)

A resin component (A) having a host group and essentially having a structural unit based on another radically polymerizable monomer, and
Containing a polymer (B) obtained by polymerizing a radically polymerizable monomer in a solution of the resin component (A),
The host group is
(wherein, R is the same or different and is a functional group X = 5 to 7 selected from the group consisting of hydrogen, an acetyl group, an alkyl group having 50 or less carbon atoms, and -CONHR (R is a methyl group or an ethyl group) )
A resin composition characterized by: 2. The resin composition according to claim 1, wherein the resin component (A) further has a guest group. The blending amounts of (A) and (B) are:
The resin composition according to claim 1 or 2, wherein (A)/((A)+(B)) (weight ratio) is 65 to 95% by weight. The resin composition according to claim 1 or 2, further comprising cellulose (C) modified with a compound having at least one functional group F selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, and an amide group. The blending amounts of (A) to (C) are:
(A)/((A)+(B)+(C))(weight ratio) is 57 to 95
(B)/((A)+(B)+(C))(weight ratio) is 4 to 35
(C)/((A)+(B)+(C))(weight ratio) is 1 to 16
The resin composition according to claim 4. 3. The resin composition according to claim 1, wherein the resin component (A) is a copolymer of a host group-containing monomer and another radically polymerizable monomer. Step (1-1) of preparing a solution of resin component (A)
Step (1-2) of adding raw material monomers for polymer (B) to the solution obtained in step (1-1), and polymerizing the composition obtained in step (1-2). Process (1-3)
The method for producing a resin composition according to claim 1 or 2, comprising: 8. The method for producing a resin composition according to claim 7, wherein step (1-2) is carried out in the presence of cellulose (C) modified with a compound having a functional group F. Step (2-1) of manufacturing a molded article containing resin component (A)
Step (2-2) of impregnating the molded article obtained in step (2-1) with the raw material monomer of polymer (B) and impregnation with the monomer obtained in step (2-2). Step (2-3) of polymerizing monomers in the resin molding to obtain polymer (B)
The method for producing a resin composition according to claim 1 or 2, comprising: The method for producing a resin composition according to claim 9, wherein step (2-1) is carried out in the presence of cellulose (C) modified with a compound having a functional group F. A resin molded article comprising the resin composition according to claim 1 or 2. A resin molded article made of the resin composition according to claim 11, having an elastic modulus of 5 to 60 MPa. The resin molded product according to claim 11, which has a toughness in a tensile test of 5 to 90 MJm-3.