JP7264368B2 - Fiber reinforced material and method for producing fiber reinforced material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a fiber reinforced material and a method for producing the fiber reinforced material.

So-called biocompatible materials, which are not rejected by living organisms, are known. Taking advantage of such properties, biocompatible materials are used as implantable medical devices such as artificial blood vessels and artificial joints. As biocompatible materials, amphoteric polyelectrolytes described in Patent Documents 1 and 2 or fiber reinforced materials using polyvinyl alcohol hydrogels are known.

Japanese Patent Publication No. 2017-531737 U.S. Pat. No. 6,855,743

Here, when the biocompatible material is used for an artificial blood vessel or the like, it is anastomosed with a surrounding blood vessel or the like. At that time, if the tear strength of the biocompatible material is low, the material is easily torn when a needle or thread is passed through the biocompatible material. Therefore, materials with high tear strength are desired as biocompatible materials.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fiber-reinforced material that can be suitably used as a biocompatible material and has high tear strength, and a method for producing the same.

The fiber-reinforced material of the present invention is a fiber-reinforced material obtained by integrating a fiber base material and a resin composition containing a polymer, wherein the polymer has an ethylenically unsaturated group and two or more hydroxyl groups. and at least one structural unit derived from the monomer (B) having an ethylenically unsaturated group and a lactam ring.

When the polymer contains 40% by mass or more of at least one of structural units derived from the monomer (A) and structural units derived from the monomer (B), based on the total amount of the polymer. preferable.

The polymer contains 0.5 to 10 parts by mass of structural units derived from a cross-linking agent with respect to a total of 100 parts by mass of structural units derived from the monomer (A) and structural units derived from the monomer (B). It is preferable to include

（式（Ｉ）中、Ｒ^１は、水素原子又はメチル基、Ｒ^２は、２個以上の水酸基を有する有機基を示す。） Preferably, the polymer contains a structural unit derived from a monomer (A), and the monomer (A) is a compound represented by the following formula (I).

(In formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an organic group having two or more hydroxyl groups.)

In formula (I), R ² is -COOR ³ groups, -OCOR ³ groups, -OR ³ groups, -CONHR ³ groups, -CH ₂ OR ³ groups, -CH ₂ OCOR ³ groups, -CONHR ³ groups, - CON(R ³ ) ₂ groups or —NHCOR ³ groups (R ³ represents an organic group having two or more hydroxyl groups) are preferred.

（式中、Ｒ^１は、水素原子またはメチル基、Ｒ^４は、炭素数１～４のアルキレン基を示す。） Monomer (A) is preferably a compound represented by the following formula (II).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkylene group having 1 to 4 carbon atoms.)

（式中、Ｒ^７、Ｒ^８、Ｒ^９は、水素原子又は置換基を有していてもよい炭素数１～１０のアルキル基であり、ｐは、０～４の整数であり、ｑは、２～６の整数であり、ラクタム環の一つ以上の水素原子が置換されていてもよい。） Preferably, the polymer contains a structural unit derived from the monomer (B), and the monomer (B) is a compound represented by the following formula (III).

(wherein R ⁷ , R ⁸ and R ⁹ are a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms, p is an integer of 0 to 4, and q is , an integer of 2 to 6, and one or more hydrogen atoms of the lactam ring may be substituted.)

Monomer (B) is selected from the group consisting of N-vinylpyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinylpiperidone, N-vinyl-ε-caprolactam, 1-(2-propenyl)-2-piperidone is preferably at least one compound that

It is preferable that the saturated water content of the resin composition at 25°C is 30% or more and less than 87%.

Preferably, the fibrous substrate is a woven, knitted or non-woven fabric.

It is preferred that the fibrous base material has a two-dimensional or three-dimensional network structure.

It is preferable that the fiber base material contains one or more selected from the group consisting of cotton, silk, yarn, cellulose fiber, polyester fiber, nylon fiber, and acrylic fiber.

The medical device of the present invention contains the fiber reinforced material.

The medical device is preferably an artificial blood vessel, a scaffolding material for tissue formation, or an anti-adhesion material.

The method for producing a fiber reinforced material of the present invention comprises a monomer (A) having an ethylenically unsaturated group and two or more hydroxyl groups, and a monomer (B) having an ethylenically unsaturated group and a lactam ring. A polymerization step of obtaining a fiber reinforcing material by heating or irradiating a fiber reinforcing material precursor obtained by impregnating a fiber base material with a monomer composition containing at least one of Prepare.

In the polymerization step, it is preferable to perform heating or light irradiation in a state in which the fiber reinforcing material precursor is impregnated with water.

In the polymerization step, it is preferable to carry out the polymerization at a temperature of 80° C. or less.

It is preferable to further include a step of immersing the fiber-reinforced material in warm water of 50° C. or higher to remove impurities.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a fiber-reinforced material that can be suitably used as a biocompatible material and has high tear strength, and a method for producing the same.

The fiber reinforced material of the present embodiment is a fiber reinforced material in which a fiber base material and a resin composition containing a polymer are integrated, and the polymer contains an ethylenically unsaturated group and two or more hydroxyl groups. and at least one structural unit derived from a monomer (B) having an ethylenically unsaturated group and a lactam ring. In addition, "integration" means that the resin composition and the fiber base material cannot be separated without destroying the fiber reinforcing material. Moreover, the fiber-reinforced material of the present embodiment tends to be excellent in tensile strength as well.

When the polymer contains 40% by mass or more of at least one of structural units derived from the monomer (A) and structural units derived from the monomer (B), based on the total amount of the polymer. It is preferably contained in an amount of 60% by mass or more, more preferably in an amount of 80% by mass or more. The content of at least one of structural units derived from the monomer (A) and structural units derived from the monomer (B) in the polymer is not particularly limited, and is 98% by mass or less. may be 95% by mass or less. In the present disclosure, the “structural unit derived from the monomer (A)” typically represents the same structural unit as the structural unit formed by polymerizing the monomer (A). In other words, the “structural unit derived from the monomer (A)” is not limited to structural units formed by the actual polymerization of the monomer (A), and may be a single unit as long as it has the same structure as them. Structural units formed by methods other than polymerizing the monomer (A) are also included in the structural units derived from the monomer (A). For example, if the structural unit is derived from a compound represented by formula (II) described later, -CH ₂ -C(-R ¹ )(-C(=O)-OR ⁴ -C(OH)CH ₂ OH)-. The same applies to structural units derived from the monomer (B).

The monomer (A) is not particularly limited as long as it has an ethylenically unsaturated group and two or more hydroxyl groups. For example, a compound represented by the following formula (I) is preferable. . These monomers may be used alone or in combination of two or more.

（式（Ｉ）中、Ｒ^１は、水素原子またはメチル基、Ｒ^２は、２個以上の水酸基を有する有機基を示す。）

(In formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an organic group having two or more hydroxyl groups.)

In formula (I), ^R2 is an organic group having two or more hydroxyl groups. Among them, from the viewpoint of improving hydrophilicity (water wettability), -COOR ³ groups, -OCOR ³ groups, -OR ³ groups, -CONHR ³ groups, -CH ₂ OR ³ groups, -CH ₂ OCOR ³ group, --CONHR ³ group, --CON(R ³ ) ₂ group or --NHCOR ³ group (R ³ represents an organic group having two or more hydroxyl groups). These monomers may be used alone or in combination of two or more.

R ³ is an organic group having 2 or more hydroxyl groups, preferably an organic group having 1 to 30 carbon atoms and having 2 or more hydroxyl groups from the viewpoint of improving hydrophilicity (water wettability), and more An organic group having 1 to 20 carbon atoms and having two or more hydroxyl groups is preferred. Examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a polyoxyalkylene group having 4 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and the like. . When two or more ^R3 's are contained in one molecule, each ^R3 may be the same or different. Further, R ³ may contain, for example, a halogen atom such as a fluorine atom or a chlorine atom, a nitrogen atom, or a functional group other than a hydroxyl group.

Examples of the monomer (A) include esters of polyhydric alcohols having three or more hydroxyl groups and (meth)acrylic acid, esters of sugars and (meth)acrylic acid, sugars having an amino group and (meth) ) and esters with acrylic acid. These esters may be prepared not only by an esterification reaction, but also by a transesterification reaction or a ring-opening reaction of glycidyl (meth)acrylate.

Examples of polyhydric alcohols having 3 or more hydroxyl groups include glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, pentaerythritol, 1,2,6-hexanetriol, and 2-hydroxymethyl-2. -methyl-1,3-propanediol, 2-ethyl-2-hydroxymethyl-1,3-propanediol, and the like. Examples of sugars include monosaccharides such as glucose, mannose, galactose, gulose, fructose, and D-ribose, glucosides, galactosides, fructosides derived from these monosaccharides, and dimers and trimers thereof. are mentioned. Sugars having an amino group include, for example, D-glucosamine.

The monomer (A) is preferably a compound represented by the following formula (II).

（式（ＩＩ）中、Ｒ^１は、水素原子またはメチル基、Ｒ^４は、炭素数１～４のアルキレン基を示す）で表わされる（メタ）アクリル酸エステルがより好ましく、親水性（水濡れ性）をより一層向上させる観点から、グリセリンモノ（メタ）アクリレートがさらに好ましい。

(In formula (II), R ¹ is a hydrogen atom or a methyl group, and R ⁴ is an alkylene group having 1 to 4 carbon atoms) is more preferably a (meth)acrylic acid ester, which is hydrophilic (water wet Glycerin mono(meth)acrylate is more preferable from the viewpoint of further improving the properties).

The molecular weight of the monomer (A) is preferably 500 or less.

Also, the monomer (A) may be represented by the following formula (IA) or (IB).

（式中、Ｒ^１は、水素原子又はメチル基を表す。Ｒ^５は、－ＣＨ_２－、－ＣＯ－又は直接結合を表す。ｎは、０～２０以下の数を表し、Ｒ^５が－ＣＯ－の場合、ｎは０ではない。ｎは、２～１５であることが好ましく、３～１０であることがより好ましい。）

（式中、Ｒ^５は、－ＣＨ_２－、－ＣＯ－又は直接結合を表す。ｍは、０～２０の数を表し、２～１５であることが好ましく、３～１０であることがより好ましい。）

(In the formula, R ¹ represents a hydrogen atom or a methyl group; R ⁵ represents —CH ₂ —, —CO— or a direct bond; n represents ^a number from 0 to 20 or less; In the case of CO—, n is not 0. n is preferably 2 to 15, more preferably 3 to 10.)

(wherein R ⁵ represents —CH ₂ —, —CO— or a direct bond; m represents a number of 0 to 20, preferably 2 to 15, more preferably 3 to 10; preferable.)

When the polymer contains a structural unit derived from the monomer (A), the content of the structural unit derived from the monomer (A) is 40% by mass or more based on the total amount of the polymer. It is preferably contained in an amount of 60% by mass or more, more preferably in an amount of 80% by mass or more. The content of structural units derived from the monomer (A) in the polymer is not particularly limited, and may be 98% by mass or less, or 95% by mass or less. When the polymer contains structural units derived from the monomer (A), the fiber-reinforced material tends to be excellent not only in tear strength but also in tensile strength.

（式中、Ｒ^７、Ｒ^８、及びＲ^９は、それぞれ、水素原子又は置換基を有していてもよい炭素数１～１０のアルキル基であり、ｐは、０～４の整数であり、ｑは、２～６の整数であり、ラクタム環の炭素原子に結合する一つ以上の水素原子が、置換基により置換されていてもよい。当該置換基は、炭素数１～１０の置換又は未置換のアルキル基であってよい。） The monomer (B) is not particularly limited as long as it has an ethylenically unsaturated group and a lactam ring in the molecule, but is preferably a compound represented by the following formula (III). One or more of the compounds represented by formula (III) can be used.

(wherein R ⁷ , R ⁸ and R ⁹ are each a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms; p is an integer of 0 to 4; , q is an integer of 2 to 6, and one or more hydrogen atoms bonded to the carbon atoms of the lactam ring may be substituted with a substituent, which is a substituent having 1 to 10 carbon atoms. or an unsubstituted alkyl group.)

The number of carbon atoms in the alkyl group for R ⁷ , R ⁸ and R ⁹ is preferably 1-6, more preferably 1-4. The alkyl group is preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Substituents for R ⁷ , R ⁸ and R ⁹ are not particularly limited, but include carboxyl group, sulfonic acid group and esters or salts thereof; amino group, hydroxyl group and the like. The number of substituents in the alkyl groups of R ⁷ , R ⁸ and R ⁹ is preferably 0 to 2, more preferably 1, for R ⁷ , R ⁸ and R ⁹ . A hydrogen atom is preferred.

In formula (III), one or more hydrogen atoms bonded to carbon atoms of the lactam ring may be substituted with a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. In other words, in formula (III), one or more substituents may be bonded to the carbon atoms of the lactam ring, and the substituents are substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms. It can be. The number of substituents bonded to the carbon atoms of the lactam ring is preferably 0 to 2, more preferably 1. The number of carbon atoms in the alkyl group which the lactam ring has as a substituent is preferably 1-6, more preferably 1-4. More specifically, the alkyl group is preferably a methyl group. When the alkyl group has a substituent, the substituent includes, but is not limited to, a carboxyl group, a sulfonic acid group, and esters or salts thereof; an amino group, a hydroxyl group, and the like. The number of substituents bonded to the alkyl group is preferably 0 to 2, more preferably 1. The lactam ring may be unsubstituted.

p is preferably an integer from 0 to 2, more preferably an integer from 0 to 1, and most preferably 0; q is preferably 2-5, more preferably 3-5.

Examples of compounds represented by the formula (III) include N-vinylpyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinylpiperidone, N-vinyl-ε-caprolactam, 1-(2-propenyl)-2-piperidone. is mentioned.

When the polymer contains a structural unit derived from the monomer (B), the content of the structural unit derived from the monomer (B) is 40% by mass or more based on the total amount of the polymer. It is preferably contained in an amount of 60% by mass or more, more preferably in an amount of 80% by mass or more. The content of structural units derived from the monomer (B) in the polymer is not particularly limited, and may be 98% by mass or less, or 95% by mass or less.

The polymer may contain a structural unit derived from a monomer (C) other than the above monomers (A) and (B). Examples of the monomer (C) include monomers having a structure in which an organic group having 4 or more carbon atoms is bonded to an ethylenically unsaturated group. Examples of such monomers include (meth)acrylic acid esters represented by formula (IC).

（式（ＩＣ）中、Ｒ^１１は、水素原子又はメチル基を表す。Ｒ^１２は、炭素が連続して４個以上結合した炭素鎖を有する有機基を表す。）で表される構造単位が好ましい。

(In the formula (IC), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² represents an organic group having a carbon chain in which 4 or more carbon atoms are continuously bonded.) preferable.

Examples of the (meth)acrylic acid ester represented by the formula (IC) include (meth)acrylic acid, n-butyl, s-butyl (meth)acrylate, t-butyl (meth)acrylate, and (meth)acrylic acid. n-amyl, s-amyl (meth)acrylate, t-amyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylate tridecyl acrylate, cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylate Phenyl acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, (meth) ) 4-hydroxybutyl acrylate, 2-ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, β-methylglycidyl (meth)acrylate, (meth)acrylic acid β-ethylglycidyl, (3,4-epoxycyclohexyl)methyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate and the like.

Among the monomers having a structure in which an organic group having 4 or more carbon atoms is bonded to the ethylenically unsaturated group, examples other than the (meth)acrylic acid ester of the formula (IC) include butyl vinyl ether and 2-ethylhexyl vinyl ether. , dodecyl vinyl ether, stearyl vinyl ether, diethylene glycol vinyl ether, triethylene glycol vinyl ether and other vinyl ethers, N-vinyls such as N-vinylmorpholine and N-vinylcarbazole (excluding those having a lactam ring), N-phenylmaleimide, N N-substituted maleimides such as -benzylmaleimide, N-naphthylmaleimide, N-cyclohexylmaleimide, N-butylmaleimide, N-isopropylmaleimide and N-ethylmaleimide.

Further, as the monomer (C), any (meth)acrylic acid selected from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate Alkyl esters; vinyl esters such as vinyl acetate and vinyl propionate; vinyl chloride, vinylidene chloride and the like; olefins such as ethylene, propylene, butene and isoprene; N-vinyl compounds such as N-vinylformamide and N-vinylacetamide; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and propyl vinyl ether; methyl maleimide and the like can also be used.

The content of structural units derived from the monomer (C) is preferably 50% by mass or less, preferably 30% by mass or less, and 10% by mass or less, relative to the total amount of the polymer. preferable.

The polymer preferably has a structure chemically crosslinked with a crosslinking agent. Examples of cross-linking agents include compounds having two or more ethylenically unsaturated groups in the molecule, such as polyfunctional (meth)acrylic acid amides and polyfunctional (meth)acrylic acid esters. In other words, it has structural units derived from compounds having two or more ethylenically unsaturated groups in the molecule, such as polyfunctional (meth)acrylic acid amides and polyfunctional (meth)acrylic acid esters. As the cross-linking agent, one or two or more can be used.

Polyfunctional (meth)acrylic esters include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, cyclohexanedimethanol diacrylate, ethoxylated bisphenol A diacrylate, tricyclodecanedimethanol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dendrimer acrylate, 1,4-butanediol dimethacrylate, 1 ,6-hexanediol dimethacrylate, triethylene glycol dimethacrylate, ethoxylated bisphenol A dimethacrylate, and trimethylolpropane trimethacrylate.

Examples of polyfunctional (meth)acrylic acid amides include N,N'-methylenebisacrylamide.

The content of the structural unit derived from the cross-linking agent in the polymer is 0 with respect to a total of 100 parts by mass of the structural unit derived from the monomer (A) and the structural unit derived from the monomer (B). .5 to 10 parts by mass, more preferably 1 to 3 parts by mass.

The polymer is preferably a crosslinked body, and the content of the non-crosslinked polymer is preferably less than 3% by mass, more preferably less than 1% by mass, based on the total amount of the polymer. When it contains a non-crosslinked polymer, it preferably has a weight average molecular weight of 1,000 to 10,000,000. When the weight average molecular weight is in such a range, the material is excellent in durability and mechanical strength, which is preferable. The weight average molecular weight is more preferably 5,000 to 2,000,000, still more preferably 10,000 to 500,000.

In the above polymer, the proportion of components having a molecular weight of 5,000 or less is preferably 5.0 mass % or less of the entire polymer. When the proportion of components having a molecular weight of 5,000 or less is 5.0% by mass or less of the total polymer, the elution of low-molecular-weight components into the blood can be suppressed even after long-term use, and affinity with living tissue is enhanced. be better. The proportion of components having a molecular weight of 5,000 or less is more preferably 1.0% or less of the total polymer, and still more preferably 0.5% by mass or less of the total polymer.
The weight average molecular weight of the polymer and the ratio of components having a molecular weight of 5000 or less can be measured by gel permeation chromatography (GPC).

The resin composition of this embodiment may be a hydrogel containing the polymer and water. The water content in the resin composition (the ratio of the mass of water to the total mass of the resin composition) is preferably 30% or more and less than 95%, preferably 50 to 90%, and more preferably 65 to 85%. preferable. In the resin composition, the total amount of the polymer and water as an optional component may be 90% by mass or more, 95% by mass or more, or 98% by mass or more of the total amount of the resin composition. .

The resin composition of the present embodiment may contain components other than the polymer and water. Components other than the polymer and water may include, for example, antioxidants, stabilizers, colorants, fragrances, thickeners, lubricants, antifoaming agents, preservatives, antibacterial agents, antifungal agents, and the like.

The moisture content of the fiber reinforced material of the present embodiment is preferably less than 95%, more preferably 90% or less, even more preferably 85% or less, and particularly preferably 80% or less. Incidentally, the moisture content of the fiber reinforced material of the present embodiment may be 30% or more, or may be 50% or more.

The moisture content of the fiber reinforced material is defined by the following formula.
(Water content [%]) = {(Water content of fiber reinforced material [g]) - (Dry weight of fiber reinforced material [g])}/(Water content of fiber reinforced material [g])
The wet mass of the fiber reinforced material is the mass of the fiber reinforced material in a state containing water. The dry weight of the fiber reinforced material is the weight after drying the fiber reinforced material and removing water. Drying of the fiber reinforced material can be performed, for example, with a hot air dryer. More specifically, the fiber reinforced material is left to stand at 120° C. for 1 hour in a hot air dryer to dry, and after standing to cool in a desiccator, the mass can be measured immediately.
The water content of the resin composition can be measured by the same method by preparing a resin composition that is not integrated with the fiber base material.

In addition, the saturated water content at 25° C. of the fiber reinforced material of the present embodiment is preferably less than 95%, more preferably 90% or less, even more preferably less than 87%, and 85% or less. More preferably, it is particularly preferably 80% or less. The saturated water content at 25° C. of the fiber reinforced material of the present embodiment may be 30% or higher, or 50% or higher.

The saturated moisture content of the fiber reinforced material is defined by the following formula.
(saturated water content [%]) = {(mass of fiber reinforced material in saturated water content [g]) - (dry mass of fiber reinforced material [g])} / (mass of fiber reinforced material in saturated water content [g ])
The mass of the fiber reinforced material in a saturated water content state can be measured, for example, as follows. First, a strip-shaped test piece having a thickness of 1.0 mm, a length of 40 mm, and a width of 10 mm is prepared from a fiber reinforced material. Next, the test piece is immersed in ion-exchanged water for 5 hours or more to make it saturated with water. Then, the mass of the test piece in the saturated water content state is measured and defined as the "water content mass". In place of the strip-shaped fiber reinforced material, a sample weighing 2 g or less (regardless of shape) can be used instead.
After that, the test piece is dried, for example, with a hot air dryer to remove moisture. More specifically, it can be dried by standing still at 120° C. for 1 hour in a hot air dryer, allowed to stand to cool in a desiccator, and then immediately measured for weight to be referred to as “dry weight”.
In addition, the saturated moisture content may be the saturated moisture content at 25°C when the step of bringing the above-described fiber reinforced material into a saturated moisture state is performed at 25°C. In addition, the step of making the above-mentioned fiber reinforced material saturated with water is performed at a temperature equal to the ambient temperature in the environment where the fiber reinforced material is placed, such as storage, transportation, and display in stores (for example, 5 to 40 ° C.). Alternatively, it may be the saturated moisture content at the ambient temperature. In this specification, when the temperature of the saturated water content is not specified, it means the saturated water content at the ambient temperature.

The moisture content of the fiber reinforced material of the present embodiment is preferably less than 90% of the saturated moisture content, more preferably 89% or less, even more preferably 88% or less, and particularly preferably 85% or less. .

The saturated water content at 25° C. of the resin composition of the present embodiment is preferably less than 95%, more preferably 94% or less, even more preferably 93% or less, and particularly preferably 90% or less. . In addition, the saturated water content at 25° C. of the resin composition of the present embodiment may be 30% or more, or may be 50% or more.

The saturated water content of the resin composition at 25°C is defined by the following formula.
(saturated water content [%]) = {(water content mass of polymer in saturated water content state [g]) - (dry mass of polymer [g])} / (water content mass of resin composition in saturated water content state [g ])
The water content mass of the resin composition in a saturated water content state is measured as follows. First, a strip-shaped test piece having a thickness of 1.0 mm, a length of 40 mm, and a width of 10 mm is prepared from a polymer. Next, the test piece is immersed in ion-exchanged water at room temperature (25° C.) for 5 hours or more to make it saturated with water. Then, the mass of the test piece in the saturated water content state is measured and defined as the "water content mass". In place of the strip-shaped test piece, a sample weighing 2 g or less (regardless of shape) can be used instead.
After that, the test piece is dried, for example, with a hot air dryer to remove moisture. The test piece is dried, for example, by leaving it to stand at 120° C. for 1 hour in a hot air dryer, cooling it in a desiccator, and immediately measuring the weight to obtain the “dry weight”. The saturated water content of the resin composition may be measured using a gel containing water (hydrogel) as the test piece.
As in the case of the fiber reinforced material, the saturated water content of the resin composition at 25°C is the saturated water content at 25°C.

The fibers contained in the fiber base material include synthetic fibers and natural fibers, and the natural fibers include chemically modified or chemically modified natural fibers, physically processed fibers, and the like. More specific examples include cotton, silk, yarn, cellulose fiber, polyester fiber, nylon fiber, acrylic fiber, carbon fiber, glass fiber, metal fiber and the like. These can use 1 type(s) or 2 or more types. The fiber base material may contain hydrophobic fibers such as polyolefin fibers, and the content thereof is preferably 20% by mass or less with respect to the total amount of the fiber base material, and may be 10% by mass or less. It may be substantially 0% by mass.

The fibrous substrate may be woven, knitted or non-woven. The fibrous substrate may be a knitted fabric or a knitted fabric. The fibrous base material may have a two-dimensional or three-dimensional network structure.

The shape of the fiber reinforced material is not particularly limited, and may be sheet-like, tube-like, or the like, depending on the application.

In the method for producing a fiber reinforced material of the present embodiment, a monomer (A) having an ethylenically unsaturated group and two or more hydroxyl groups, and a monomer (B A fibrous reinforcing material precursor obtained by impregnating a fibrous base material with a monomer composition containing at least one of (1) above is heated or irradiated with light to polymerize the monomer composition to obtain a fibrous reinforcing material. Have a process.

The monomer composition contains at least one of the monomer (A) and the monomer (B), and a polymerization initiator, and optionally contains the above-mentioned cross-linking agent, monomer (C), etc. good. The content of the monomer (A), the monomer (B), the monomer (C) and the cross-linking agent in the monomer composition is the content of structural units derived from each monomer contained in the polymer. Blend so that the amount is the desired content.

A fibrous base material is impregnated with the monomer composition to prepare a fibrous reinforcing material precursor. At this time, the monomer composition may be impregnated in the form of an aqueous solution. Alternatively, the fibrous reinforcing material precursor may be formed by spraying the monomer composition in the form of an aqueous solution onto the fibrous base material. In these cases, in the polymerization step, the polymerization reaction can be carried out while the fiber reinforcing material precursor contains water.
The amount of water relative to the monomer composition may be 40 to 900 parts by weight, or 100 to 600 parts by weight, per 100 parts by weight of the monomer composition.

A polymerization initiator generates radicals by heat or light and can initiate a radical polymerization reaction. The polymerization initiator is not particularly limited, but hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate; dimethyl 2,2′-azobis(2-methylpropionate), 2,2 Azo compounds such as '-azobis(isobutyronitrile), 2,2-azobis(2-methylpropionamidine) dihydrochloride; organic peroxides such as benzoyl peroxide, peracetic acid, and di-t-butyl peroxide Goods and the like are preferred. These polymerization initiators may be used alone or in the form of a mixture of two or more.

The temperature in the polymerization process is preferably 80°C or less, more preferably 40°C to 70°C. The polymerization reaction may be carried out under normal pressure (1 atm), increased pressure, or reduced pressure.

It is preferable that the production method of the present embodiment further include a step of immersing the obtained fiber reinforced material in warm water of 50° C. or higher to remove impurities. The temperature of the warm water is more preferably 60°C or higher, and even more preferably 70°C or higher.

Since the fiber reinforced material of the present embodiment has excellent tear strength, it can be used in various applications that could not be applied to hydrogels. It is also preferable to use it in the form of a sheet by attaching it to a surface to be water-retained, or by winding or wrapping an article. It is suitable for food packaging, various protective sheets, water-retaining materials, cushioning materials, moisture-supplying sheets, sustained-release drug sheets, cosmetic sheets, and toys. Moreover, it can be used after shaping into a sheet shape, tubular shape, or other desired shape.

Since the fiber reinforced material of the present embodiment has excellent biocompatibility, it can be suitably used as a material for medical devices. The fiber reinforced material of the present embodiment can be suitably used as an anti-thrombotic material that does not readily form thrombi even when in contact with blood, and can be used as a material for forming portions of various medical devices that come into contact with biological components or biological tissues. can also be preferably used. Furthermore, the fiber reinforced material of this embodiment can also be suitably used as a cell culture substrate.

When the fiber reinforced material of the present embodiment is used as a medical device, specifically, for artificial biological tissues such as artificial blood vessels and artificial organs, blood filters, various catheters, various stents, etc.; as a member for a cell culture substrate, a member for a hemodialysis device, a member for blood or tissue examination instruments, etc.; can. In addition, the fiber-reinforced material of the present embodiment can also be used as a scaffold material for tissue formation, an anti-adhesion material, a burn treatment material, and a wound treatment material. That is, the medical device of the present embodiment includes devices that come into contact with living tissue, devices that come into contact with biological components (cells, blood, etc.), and the like.

[Method for producing fiber reinforced material]
A U-shaped spacer made of a Teflon sheet with a thickness of 0.4 mm was placed on the polypropylene plate. A gauze was laid as a fiber base inside the region surrounded by the U-shaped spacers. An aqueous solution of the monomer composition having the composition shown in Table 1 was poured onto the fiber base material, and the fiber base material was immersed in the aqueous solution. Another polypropylene plate was placed on top, and the two polypropylene plates were fixed with a clamp while sandwiching a spacer. In this state, a casting frame composed of two polypropylene plates was formed with a spacer interposed therebetween, and the inside of the frame was filled with the fiber base material and the aqueous monomer solution. After defoaming the aqueous solution of the monomer composition by vibrating the casting mold with a vibrator, the solution was allowed to stand in a hot air dryer at 60° C. for 1 hour to gel the aqueous solution of the monomer composition. After that, the clamps of the casting frame were removed, and the fiber reinforced material (fiber reinforced gel sheet) was taken out. The fiber-reinforced gel sheet was immersed in a container containing ion-exchanged water at about 60° C. and kept at 60° C. for 5 hours with gentle stirring to extract and remove impurities. Further, the fiber-reinforced gel sheet was immersed in deionized water at room temperature to sufficiently absorb water. As a result, fiber-reinforced gel sheets of Examples 1-3 and Comparative Examples 1-2 were obtained.

<Evaluation method>
[Saturated moisture content]
A gel sheet of a resin composition was produced in the same manner as in Examples 1-3 and Comparative Examples 1-2, except that the fiber base material was omitted. A gel sheet of the resin composition was immersed in ion-exchanged water at 25° C. for 5 hours or longer to be saturated with water, and the mass was measured to obtain the water-containing mass. Thereafter, the gel sheet was left to stand in a hot air dryer at 120° C. for 1 hour to dry, allowed to cool in a desiccator, and immediately weighed to obtain a dry weight. The saturated water content was obtained from the following formula.
(saturated water content [%]) = {(wet weight [g]) - (dry weight [g])} / (wet weight [g])

[Tensile strength]
The fiber-reinforced gel sheets of Examples 1-3 and Comparative Examples 1-2 were immersed in ion-exchanged water for 5 hours or longer to be saturated with water, and then cut into strips with a width of 10 mm and a length of 40 mm to obtain test pieces. The sample was pulled at a distance between chucks of 20 mm and a tensile speed of 50 mm/min, and the tensile force at breakage was measured as the tensile strength. The test pieces were stored in ion-exchanged water until just before the tensile test. Table 1 shows the results.

[Tear strength]
The fiber reinforced gel sheets of Examples 1 to 3 and Comparative Examples 1 and 2 were immersed in ion-exchanged water for 5 hours or longer to be saturated with water, and then cut into strips having a width of 20 mm and a length of 40 mm to obtain fiber reinforced gel sheet pieces. made. A cut was made in the lower half of the fiber-reinforced gel sheet piece parallel to the longitudinal direction from one longitudinal end of the fiber-reinforced gel sheet piece to the other end of the fiber-reinforced gel sheet piece to obtain a test piece. That is, the test piece is bifurcated with a width of 10 mm and a length of 20 mm only at the lower portion. The tear strength was measured by tearing at a chuck-to-chuck distance of 20 mm and a tensile speed of 50 mm/min. Table 1 shows the results.

[Complement activity]
Samples were immersed in human serum and incubated at 37° C. for 1 hr. After completion of the incubation, the mixture was centrifuged at 4° C. and 3500 rpm for 10 minutes, the supernatant was removed, and an ELISA (enzyme-linked immunosorbent assay) measurement was performed. Complement factor SC5b-9 (manufactured by QUIDEL Corporation, trade name: MICROVUE SC5b-9 Plus EIA) was measured by ELISA according to the instructions attached to the ELISA kit. A high-density polyethylene film (sterilized with ethylene oxide gas) was used as a negative control substance, and cellulose (manufactured by Regenerated Cellulose, trade name: Whatman RC55 Membrane Filters) was used as a positive control substance. Three samples were measured, and the average value of the three measured values was used as the measured value. Complement activation value was calculated from the following formula, and A was determined when the complement activation value was 5% or less, and B was determined when the complement activation value was greater than 5 and 30% or less. Complement activation value indicates that biocompatibility is better as the value is lower. Table 1 shows the results.
[Complement activation value (%)] = {(measured value of sample) - (measured value of negative control substance)} / {(measured value of positive control substance) - (measured value of negative control substance)} x 100

Abbreviations used in Table 1 are as follows.
GLMA: glycerin monoacrylate NVP: N-vinylpyrrolidone HEMA: 2-hydroxyethyl methacrylate MBAAm: N,N'-methylenebisacrylamide (crosslinking agent)
V-50: 2,2-azobis (2-methylpropionamidine) dihydrochloride (polymerization initiator, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name)
Gauze: Yokoi Co., Ltd. (cotton, 2-ply)
Non-woven fabric: Bemliese SE803 manufactured by Asahi Kasei Fibers Co., Ltd. (made of cellulose, 1 ply)

As a reference example in Table 1, the tensile strength and tear strength were the same as those of the fiber-reinforced gel sheets of Examples and Comparative Examples, except that the gel was not integrated with the fiber base material (that is, only the fiber base material was used). was measured. Table 1 shows the results.

In Comparative Example 1, which was not integrated with the resin composition, the strength was so low that the tear strength could not be measured. In addition, as shown in Reference Example 1, the gauze alone deformed the test piece into a filamentous shape, and the tear strength could not be measured. On the other hand, in Example 1 in which the resin composition and gauze (fiber base material) are integrated, it has a higher tear strength than Comparative Example 1 and Reference Example 1, and is also excellent in tensile strength. The biocompatibility was also sufficient from the value of .
In Example 2, in which the resin composition and the nonwoven fabric (fiber base material) are integrated, the tensile strength and tear strength are superior to those of Reference Example 2 in which only the nonwoven fabric is used, and the value of the complement activation value indicates sufficient biocompatibility. Met.
Example 3 in which the resin composition and the nonwoven fabric (fiber base material) were integrated also showed sufficient tensile strength and tear strength, and the value of the complement activity value showed sufficient biocompatibility.
On the other hand, in Comparative Example 2 using 2-hydroxyethyl methacrylate as a monomer, the tensile strength and tear strength were sufficient, but the biocompatibility was insufficient compared to Examples 1-3.

Claims (16)

A fiber reinforced material in which a fiber base material and a resin composition containing a polymer are integrated,
The polymer comprises a structural unit derived from a monomer (A) having an ethylenically unsaturated group and two or more hydroxyl groups, and a monomer (B) having an ethylenically unsaturated group and a lactam ring Having at least one structural unit of the structural units derived from
When the polymer contains a structural unit derived from the monomer (A), the structural unit derived from the monomer (A) is a structural unit represented by the following formula (II), the following formula (IA) and at least one selected from the group consisting of structural units represented by the following formula (IB),
When the polymer has a structural unit derived from the monomer (B), the polymer further has a structural unit derived from a cross-linking agent, and the cross-linking agent comprises polyfunctional (meth)acrylic acid amide and poly A fiber-reinforced material containing at least one functional (meth)acrylic acid ester .

(In formula (II), R ¹ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkylene group having 1 to 4 carbon atoms.)

(In formula (IA), R ¹ represents a hydrogen atom or a methyl group, R ⁵ represents —CH ₂ —, —CO— or a direct bond, n represents a number from 0 to 20 or less, R If ⁵ is -CO-, then n is not 0.)

(Wherein, R ⁵ represents —CH ₂ —, —CO— or a direct bond. m represents a number from 0 to 20.) The polymer contains at least one of structural units derived from the monomer (A) and structural units derived from the monomer (B) in an amount of 40% by mass or more, based on the total amount of the polymer. The fiber reinforced material of claim 1, comprising: The polymer contains 0.5 to 10 structural units derived from a cross-linking agent with respect to a total of 100 parts by mass of structural units derived from the monomer (A) and structural units derived from the monomer (B). The fiber reinforced material according to claim 1 or 2, comprising parts by mass. The fiber reinforced material according to any one of claims 1 to 3 , wherein the polymer comprises structural units represented by formula (II) . the polymer comprises a structural unit derived from the monomer (B),
The fiber-reinforced material according to any one of claims 1 to 4 , wherein the monomer (B) is a compound represented by the following formula (III).

(wherein R ⁷ , R ⁸ and R ⁹ are a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms, p is an integer of 0 to 4, and q is , an integer of 2 to 6, and one or more hydrogen atoms of the lactam ring may be substituted by a substituent.) Monomer (B) is selected from the group consisting of N-vinylpyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinylpiperidone, N-vinyl-ε-caprolactam, 1-(2-propenyl)-2-piperidone 6. The fiber reinforced material according to claim 5 , which is at least one compound that is The fiber reinforced material according to any one of claims 1 to 6 , wherein the resin composition has a saturated water content of 30% or more and less than 87% at 25°C. The fiber reinforced material according to any one of claims 1 to 7 , wherein said fiber base material is a fabric, knitted fabric or non-woven fabric. The fiber reinforced material according to any one of claims 1 to 8 , wherein the fiber base material has a two-dimensional or three-dimensional network structure. The fiber according to any one of claims 1 to 9 , wherein the fiber base material contains one or more selected from the group consisting of cotton, silk, yarn, cellulose fiber, polyester fiber, nylon fiber, and acrylic fiber. reinforced material. A medical device comprising the fiber reinforced material according to any one of claims 1-10 . 12. The medical device according to claim 11 , which is an artificial blood vessel, a scaffolding material for tissue formation, or an anti-adhesion material. A monomer composition containing at least one of a monomer (A) having an ethylenically unsaturated group and two or more hydroxyl groups and a monomer (B) having an ethylenically unsaturated group and a lactam ring A polymerization step of heating or irradiating the fiber reinforcing material precursor impregnated into the fiber base material to polymerize the monomer composition to obtain a fiber reinforcing material ,
A method for producing a fiber-reinforced material, wherein in the polymerization step, the heating or light irradiation is performed in a state in which the precursor of the fiber-reinforced material contains water . The method for producing a fiber-reinforced material according to claim 13 , further comprising a step of immersing the fiber-reinforced material in warm water of 50°C or higher to remove impurities. A monomer composition containing at least one of a monomer (A) having an ethylenically unsaturated group and two or more hydroxyl groups and a monomer (B) having an ethylenically unsaturated group and a lactam ring A polymerization step of heating or irradiating the fiber reinforcing material precursor impregnated into the fiber base material to polymerize the monomer composition to obtain a fiber reinforcing material;
A method for producing a fiber-reinforced material, comprising a step of immersing the fiber-reinforced material in hot water of 50° C. or higher to remove impurities . The method for producing a fiber-reinforced material according to any one of claims 13 to 15, wherein in the polymerization step, polymerization is performed at a temperature of 80°C or less.