JP2000202953A - Car interior material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a car interior material successively keeping high antibacterial/antifungal properties, not generating discoloration or staining and excellent in environmental resistance. SOLUTION: A car interior material has a sheet member having a layer containing a polymeric substance having at least one of an ammonium base, a phosphonium base and a sulfonium base in its molecular chain as an org. antibacterial/antifungal component, a layer containing the polymeric substance, a hydrophilic substance and, if necessary, a curing agent or a layer containing the polymeric substance to which the hydrophilic substance is bonded and, if necessary, the curing agent or these any layers on at least a part of the surface thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an interior material for automobiles, which is attached to an automobile or the like and in which an occupant comes into direct contact with a finger or the like, has antibacterial properties and fungicidal properties, and has water resistance and weather resistance. The present invention also relates to an interior material for automobiles having excellent solvent resistance, abrasion resistance and the like (hereinafter, these are collectively referred to as “environmental resistance”).

[0002] The automotive interior materials to which the present invention is applied include, for example, door trims, rear panels, pillar trims, instrument panels, armrests, and the like.
Headrests, glove boxes, console boxes, seats, floor mats, steering wheels, shift knobs, assist grips, door grips, seat buckles, rearview mirrors, sun visors, console lids, console panels, air direction adjustments for air conditioning outlets or opening and closing door operations Knobs, horn switch operating units, ceiling materials, etc.

[0003]

2. Description of the Related Art Currently used antibacterial materials are chitin,
Natural products such as chitosan, wasabi extract, mustard extract, hinokitiol, tea extract antibacterial material, inorganic compounds such as titanium oxide particles, ultrafine particles of zinc oxide, zeolite containing silver, zirconium phosphate containing silver, and organic compounds Synthetic products such as ammonium salts and organic phosphonium salts can be used.

[0004] Of these, natural products and inorganic products are:
Recently, attention has been paid to safety. On the other hand, organic synthetic products generally have better antibacterial activity than natural products and inorganic products, but antibacterial materials tend to volatilize and separate easily, and tend to be avoided because of their toxicity. This is because the organic synthetic antibacterial material is easily dissolved in water, an organic solvent, or the like.

For this reason, recently, an insoluble, non-toxic, immobilized antibacterial material in which an organic antibacterial material is bonded to a polymer material by an ionic bond or a covalent bond has been disclosed in JP-A-54-865.
No. 84, JP-A-04-266912, JP-T 04-814365, JP-A-05-310820
No., published in Japanese Unexamined Patent Publication No. These immobilized antibacterial materials are antibacterial materials obtained by immobilizing a quaternary ammonium base, which is ionically bonded to an acidic group such as a carboxyl group or a sulfonic acid group, on a polymer substance, and phosphonium salts immobilized on a polymer substance. An antibacterial material comprising a phosphonium salt-based vinyl polymer; an antibacterial material comprising a vinylbenzylphosphonium salt-based vinyl polymer; and an antibacterial material having a phosphonium base ion-bonded to an acidic group immobilized on a polymer substance.

However, there is no example in which these organic immobilized antibacterial materials are used as interior materials for automobiles, and these organic immobilized antibacterial materials effectively impart antibacterial and antifungal properties to interior materials for automobiles. Nothing is described in the above-mentioned publications as to whether or not the method is suitable.

[0007] In particular, the interior of a car is subject to a severe temperature change from high to low temperature depending on the climate and the season, and condensation due to the temperature change. In addition, antibacterial and
The fungicide must maintain stable antibacterial and antifungal properties even under such severe conditions. In addition, from the viewpoint of the interior of the vehicle interior, the constituent materials of the interior material must not cause discoloration or stains.

Therefore, there is no prediction as to whether the organic insoluble immobilized antibacterial material conventionally used is suitable for producing automobile interior materials having antibacterial and antifungal properties. It is something that does not connect.

[0009] The interior material for automobiles having antibacterial properties includes:
It has been conventionally known that the antibacterial material component is obtained by supporting silver ions having antibacterial properties on an inorganic porous material such as zeolite (for example, JP-A-08-24530).
No. 1, JP-A-09-100409, JP-A-H09-100409
No. 9-216563). However, a silver-based antibacterial material such as a silver-containing zeolite is not preferable because it is colored black when melted or kneaded, or changes color when irradiated with light. Further, there is a problem that the antibacterial property decreases with time.

[0010]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks of the prior art, and high antibacterial and antifungal properties are continuously maintained, and there is no occurrence of discoloration and spotting.
Another object of the present invention is to provide an automotive interior material having excellent environmental resistance.

[0011]

The object of the present invention is achieved by the following means.

1. An automotive interior material mounted in an automobile interior, wherein at least a part of the surface contains a polymer substance having at least one selected from the group consisting of ammonium base, phosphonium base and sulfonium base in a molecular chain. An interior material for automobiles, comprising:

2. An interior material for an automobile to be mounted in an automobile interior, at least a part of a surface of which is attached with a sheet-like member, and at least a part of the surface of the sheet-like member, with an ammonium base, a phosphonium base and An automotive interior material having a layer containing a polymer substance having at least one selected from the group consisting of sulfonium bases in the molecular chain.

3. Ammonium base, a layer containing a polymer substance having at least one selected from the group consisting of phosphonium base and sulfonium base in the molecular chain,
3. The automotive interior material according to the above item 1 or 2, further comprising a hydrophilic substance in a form mixed with the polymer substance.

4. Ammonium base, a layer containing a polymer substance having at least one selected from the group consisting of phosphonium base and sulfonium base in the molecular chain,
The above-mentioned item 1 or 2, further comprising a hydrophilic substance in a form chemically bonded to the polymer substance.
Automotive interior materials as described.

5. An organic compound in which a hydrophilic substance contains two or more hydrophilic groups in one molecule, such as a hydroxyl group, an amino group, an amide group, a carboxyl group or an alkali metal salt thereof, a sulfonic acid group or an alkali metal salt thereof, and an ether bond; 5. The automotive interior material according to the above item 3 or 4, which is a polymer compound.

6. The hydrophilic substance is a vinyl-based polymer having a hydrophilic group in a side chain, and the vinyl-based polymer is obtained by graft-polymerizing the constituent monomer to the polymer substance. The automotive interior material according to 3 or 4.

[7] A layer containing a polymer having at least one selected from the group consisting of ammonium base, phosphonium base and sulfonium base in the molecular chain, and a layer further containing a hydrophilic substance, further comprising at least one of a polymer substance and a hydrophilic substance 7. The interior material for an automobile according to any one of the above items 3 to 6, further comprising a curing agent capable of reacting with.

8. (7) The curing agent as described in (7) above, wherein the curing agent is a curing agent having an isocyanate group, and the interior material for an automobile has at least one resin selected from the group consisting of polyurethane, polypropylene and polyester as a constituent resin. Automotive interior materials as described.

Next, the present invention will be described in detail.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The interior material for automobiles of the present invention is basically an antibacterial material comprising a polymer having at least one selected from the group consisting of the ammonium base, phosphonium base and sulfonium base in its molecular chain. A mold-resistant resin composition layer is formed on at least a part of the surface of the vehicle interior material, or a sheet-like member having the layer on the surface is formed on at least one surface of the vehicle interior material. It is obtained by sticking to the part.

[0022] In the organic antibacterial and antifungal agent component present invention, an organic antibacterial and antifungal agent component, ammonium salt, at least one selected from the group consisting of a phosphonium salt and sulfonium salt, a polymer having a molecular chain Substance. Usually, such a high molecular substance is a high molecular substance having a low molecular weight organic compound having antibacterial properties in a molecular chain.

As the low molecular weight organic compound having antibacterial properties, those conventionally used as antibacterial agents can be used in a wide range. For example, quaternary ammonium salts such as allyl isothiocyanate, polyoxyalkylene trialkylammonium, and benzalkonium chloride, organic silicon quaternary ammonium salts, tri-n-butylhexadecylphosphonium chloride, and tri-n-butyltetradecyl Examples include, but are not limited to, quaternary phosphonium salts such as phosphonium chloride and tri-n-butylhexadecylphosphonium chloride, tetraalkyl phosphonium salts of sulfoisophthalic acid and diesters thereof.

Among these organic antibacterial agents, in particular,
Most preferred are phosphonium salt compounds having high antibacterial and antifungal activities and a broad antibacterial spectrum.

High molecular weight compound with antibacterial / antifungal compound
To bind the antibacterial / fungicidal compound to the polymer substance, for example, it may be carried out according to a known method as described in JP-A-54-86584. What is necessary is just to make a reactive functional group (for example, an acidic group) react with a high molecular substance.

In any case, in the resulting product:
The antibacterial / antifungal compound is bound to the obtained antibacterial / antifungal polymer at a rate of about 0.01 to 10% by weight, preferably about 0.05 to 5% by weight. Is preferred.

When the antibacterial and fungicidal compound is a compound containing an onium base, the compound containing the onium base and a monomer containing an acid group such as a carboxyl group, a sulfone group, a phosphone group, and a phosphine group are used. (Eg, (meth) acrylic acid, itaconic acid, styrenesulfonic acid, vinylsulfonic acid, allylphosphonic acid, 1-phenylvinylphosphonic acid, etc.) to form a monomer that is ionically bonded, and polymerize or copolymerize the monomer. The method can be adopted.

The polymer substance of the present invention may be any polymer compound as long as it has an organic antibacterial component in the molecular chain. Specific examples are shown below, but the present invention is not limited to these examples.

The antibacterial / antifungal polymer substance in a preferred embodiment of the present invention is a polymer substance containing an acid group and a phosphonium base ionically bonded to the acid group.

In a further preferred embodiment, a polyester resin containing a dicarboxylic acid component and a glycol component as main components, wherein a phosphonium salt of a sulfonic acid group-containing aromatic dicarboxylic acid represented by the following general formula (1) is used: ,
1 to 50 mol%, preferably 3 to 20 mol% based on the total acid component
It is a polyester resin copolymerized by mol%.

[0031]

Embedded image

(Wherein A represents an aromatic group, X1 and X1
2 represents an ester-forming functional group. R1, R2, R3 and R4 each represent an alkyl group, and at least one of them is an alkyl group having 10 to 20 carbon atoms. Examples of the aromatic ring constituting the trivalent aromatic group represented by A include a benzene ring and a naphthalene ring.

Examples of the ester-forming functional groups represented by X1 and X2 include a carboxyl group, a C1-C4 alkoxycarbonyl group, a hydroxyl group, a C1-C4 alkoxyl group, and a halogen atom.

The alkyl groups represented by R1, R2, R3 and R4 have 1 to 20 carbon atoms.
However, at least one of R1, R2, R3 and R4
Each has 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms.
Is an alkyl group.

Examples of the phosphonium salt of a sulfonic acid group-containing aromatic dicarboxylic acid represented by the above general formula (1) include tri-n-butyldecylphosphonium sulfoisophthalate and tri-n-butyloctadecyl sulfoisophthalate. Phosphonium salt sulfoisophthalic acid tri-n-
Butyloctadecylphosphonium salt, tri-n-butyloctadecylphosphonium sulfoisophthalate, tri-n-butylhexadecylphosphonium sulfoisophthalate, tri-n-butyltetradecylphosphonium sulfoisophthalate, n-butyl sulfoisophthalate Dodecylphosphonium salt, 4-sulfonaphthalene-2,
Tri-n-butyldecylphosphonium 7-dicarboxylate, tri-n-butyloctadecylphosphonium 4-sulfonaphthalene-2,7-dicarboxylate, tri-n-butylhexa-4-sulfonaphthalene-2,7-dicarboxylate Decylphosphonium salt, 4-sulfonaphthalene-
Tri-n-butyltetradecylphosphonium 2,7-dicarboxylate; tri-n-butyldodecylphosphonium 4-sulfonaphthalene-2,7-dicarboxylate; and the like from the viewpoint of antibacterial activity. −
n-butylhexadecylphosphonium salt, tri-n-butyltetradecylphosphonium sulfoisophthalate,
Tri-n-butyldodecylphosphonium sulfoisophthalate is particularly preferred.

The phosphonium salt of an aromatic dicarboxylic acid may be a sulfoaromatic dicarboxylic acid or its sodium, potassium or ammonium salt, or the like, as well as tri-n-butylhexadecylphosphonium bromide, tri-n-butyltetradecylphosphonium bromide, Tri-n-
It is obtained by reacting a phosphonium salt such as butyldodecylphosphonium bromide.

As the dicarboxylic acid component and the glycol component forming the polyester containing the phosphonium salt of the sulfonic acid group-containing aromatic dicarboxylic acid represented by the general formula (1), those having a wide range can be used. Can be exemplified.

(A) Dicarboxylic Acid Component As the dicarboxylic acid component to be used, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,3
-Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like.

In addition, as long as the effects of the present invention are not impaired,
An alicyclic dicarboxylic acid, an aliphatic dicarboxylic acid, a heterocyclic dicarboxylic acid and the like may be used in combination.

(B) Glycol Component As the glycol component, ethylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, 1,6-hexanediol, 1,5-pentanediol, 3-methyl1,5 -Pentanediol, 1,4-
And cyclohexanedimethanol.

Further, as long as the effects of the present invention are not impaired,
Polyhydric polyols such as trimethylolethane, trimethylolpropane, glycerin and pentaerythritol may be used in combination.

Further, the monomer represented by the above general formula (1)
The method of copolymerizing the components (a) and (b) is not particularly limited, but directly reacting dicarboxylic acids and glycols,
The so-called direct polymerization method in which the obtained oligomer is polycondensed, the so-called transesterification method in which a dimethyl ester of dicarboxylic acid and a glycol are subjected to a transesterification reaction and then polycondensed, and the like are exemplified.

In addition, as one of the high molecular substances to which the antibacterial and antifungal components are bonded, there is a phosphonium salt-based vinyl polymer represented by the following general formula (2).

[0044]

Embedded image

(Wherein R5, R6 and R7 are a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms,
An alkyl group, an aryl group (especially a phenyl group) or an aralkyl group (especially a phenyl group), which is an aryl group having 6 to 18 carbon atoms (especially a phenyl group) or substituted by a hydroxy group or an alkoxy group having 1 to 18 carbon atoms. C1-C
X ⁻ represents an anion, and n represents 2
The following integers are shown. Examples of the above R5, R6 and R7 include alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, and aryl groups such as phenyl, tolyl and xylyl. (Especially, a phenyl group or an alkyl group having 1 to 3 carbon atoms is 1 to
Particularly preferred are an aralkyl group such as benzyl and phenethyl substituted with three), an alkyl group or an aryl group substituted with a hydroxyl group, an alkoxy group and the like. R5, R6 and R7 may be the same or different groups.

X ^- is an anion such as fluorine,
Examples thereof include halogen ions such as chlorine, bromine and iodine, sulfate ions, phosphate ions, perchlorate ions and the like. Of these, halogen ions are preferable. n is not particularly limited, but is 2 to 500, preferably 10 to 300.

[0047] According to a preferred embodiment of a hydrophilic substance present invention, as described above, antibacterial and antifungal polymer materials having attached organic antibacterial agent component is a component of the resin composition of the present invention, hydrophilic Mixing or chemically binding the active substances. According to this preferred embodiment, the presence of the hydrophilic substance significantly improves the antibacterial property as compared with the case where the hydrophilic substance is not used.

The hydrophilic substance in the present invention is a substance having an excellent affinity for water, for example, a hydroxyl group, an amino group, an amide group, a carboxyl group or an alkali metal salt thereof, a sulfonic acid group or an alkali metal thereof. An organic compound or a polymer compound containing two or more hydrophilic groups such as a salt and an ether bond in one molecule.

Specific examples thereof include polyvinyl alcohol, starch or water-soluble modified starch, homopolymer or copolymer of acrylic acid, homopolymer or copolymer of methacrylic acid, homopolymer or copolymer of maleic anhydride ( For example, maleic anhydride / styrene copolymer), vinyl sulfonic acid or its copolymer or an alkali metal salt thereof, polyethylene glycol (also known as polyethylene oxide), polypropylene glycol, polyethylene / propylene glycol, polytetramethylene glycol Alkylene glycol, glycerin,
Examples thereof include polyols such as polyglycerin and polymers thereof.

Examples of the water-soluble modified cellulose include, for example, hydroxyethyl cellulose, methyl cellulose,
Methyl hydroxypropyl cellulose, sodium carboxycellulose, cellulose nitrate carboxyl methyl ether and the like can be mentioned.

Examples of the comonomer constituting the copolymer include styrene, C1-C4 alkyl acrylate, C1-C4 alkyl methacrylate, etc., and the content of these comonomers in the copolymer. Is preferably in an amount of about 10 to 50% by weight based on the copolymer.

In the present invention, at least one of these hydrophilic substances is used by being mixed or copolymerized with a polymer substance to which the organic antibacterial agent is bound.

Although the molecular weight of the hydrophilic substance is not particularly limited, the number average molecular weight is preferably 200 or more and 30,000 or less, more preferably 1,000 or more and 25,000 or less. When the hydrophilic substance is used, its content is up to 60% by weight, particularly 5 to 60% by weight, preferably 10 to 50% by weight, more preferably, to the polymer substance to which the organic antibacterial agent is bound. Is 15 to 35% by weight. In general, a further improvement of the antibacterial effect is manifested when the content of the hydrophilic substance exceeds 5% by weight. On the other hand, 60% by weight
When the ratio exceeds the above range, the mechanical properties and the heat resistance and weather resistance of the antibacterial composition tend to decrease.

When a hydrophilic substance is mixed with a polymer substance to which an organic antibacterial agent is bound, the mixing method is not particularly limited.
Any method can be adopted depending on the manufacturing method, chemical properties, physical properties, and the like. For example, a method in which both are heated and melt-mixed using an extruder, or a method in which a polymer substance and a hydrophilic substance combined with an organic antibacterial agent are mixed in a suitable solvent, for example, water, a water / alcohol mixed solvent, acetone, methyl ethyl ketone. And dissolving or dispersing in an organic solvent such as cyclohexanone, and then distilling off the solvent.

As a specific example of a method of copolymerizing a hydrophilic substance with a polymer substance to which an organic antibacterial agent is bound, for example, the main chain or side chain of a polymer substance containing a phosphonium base may be Hydroxy, amino, amide,
A monomer containing a hydrophilic group such as a carboxyl group or an alkali metal salt thereof, a sulfonic acid group or an alkali metal salt thereof can be copolymerized. By copolymerizing,
The compatibility is improved, and the appearance, storage stability, and physical properties of the coating film are improved.

As a method of copolymerizing these hydrophilic group-containing monomers, metal salts such as 5-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5 (4-sulfophenoxy) isophthalic acid, -Sulfo-
Polyester resin in which a dicarboxylic acid or glycol containing a metal salt of a sulfonic acid such as a metal salt such as 1,4-butanediol and 2,5-dimethyl-3-sulfo-2,5-hexanediol is combined with an antibacterial agent component And a method of copolymerizing an alkylene glycol such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol with a polyester resin to which an antibacterial agent component is bonded.

In the present invention, a method in which a vinyl monomer containing a hydrophilic group is graft-polymerized to a polymer substance such as a polyester resin bonded with an organic antibacterial agent can also be used.

In the present invention, examples of the vinyl monomer having a hydrophilic group capable of being graft-polymerized to a polymer substance to which an organic antibacterial agent is bound include those containing a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group, and the like. Groups that can be converted into hydrophilic groups include those containing an acid anhydride group, a glycidyl group, a chloro group, and the like. Among them, those having a carboxyl group are most preferred.

Examples of the vinyl monomer containing a hydrophilic group include monomers containing a carboxyl group or a salt thereof such as acrylic acid, methacrylic acid and salts thereof, methyl acrylate, ethyl acrylate, n-propyl acrylate and isopropyl acrylate. , N-butyl acrylate, alkyl acrylates such as t-butyl acrylate, especially C1-C4 alkyl acrylate,
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and t-butyl methacrylate, particularly C1-C4 alkyl methacrylate, 2-hydroxyethyl acrylate,
Hydroxy-containing monomers such as hydroxyethyl methacrylate, especially C1-C4 hydroxyalkyl (meth) acrylate, acrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethylacrylamide, N-methoxymethyl methacrylamide, N, N dimethylolacrylamide, N
Amide group-containing monomers such as phenylacrylamide,
In particular, it may have one or two substituents selected from the group consisting of a C1-C4 alkyl group, a C1-C4 alkoxy group, a C1-C4 hydroxyalkyl group and a phenyl group on the nitrogen atom (meta ) Epoxy-containing vinyl monomers such as acrylamide, glycidyl acrylate and glycidyl methacrylate. Other vinyl monomers having a hydrophilic group include, for example, epoxy group-containing monomers such as allyl glycidyl ether, vinyl monomers containing a sulfonic acid group such as styrene sulfonic acid, vinyl sulfonic acid and salts thereof or salts thereof. And vinyl monomers containing a carboxyl group or a salt thereof such as crotonic acid, itaconic acid, maleic acid, fumaric acid and salts thereof, and vinyl monomers containing an acid anhydride such as maleic anhydride and itaconic anhydride.

These vinyl monomers having a hydrophilic group can be used in combination with other monomers, if necessary. Other monomers include, for example, vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, acrylonitrile, methacrylonitrile, vinylidene chloride, vinyl acetate, vinyl chloride, and the like. Copolymerization can be performed using the type.

The ratio of the monomer having a hydrophilic group (Mh) to the other monomer (Ma) is represented by a molar ratio of Mh / M
a = 30/70 to 100/0 is preferable.

A known graft polymerization method can be used as a method for grafting a monomer containing a hydrophilic group (and another monomer as necessary) to a polymer substance. The following method is mentioned as a typical example.

For example, a radical polymerization method in which radicals are generated in a polymer of the main chain by light, heat, radiation or the like and then graft-polymerized with a monomer, or AlCl ₃ , TiCl ₄
And the like, and a cation polymerization method of generating a cation using a metal such as metal Na, Li or the like.

Further, there is a method in which a polymerizable unsaturated double bond is introduced in advance into a main chain polymer substance, and a vinyl monomer is graft-polymerized to the polymerizable unsaturated double bond. Examples of the monomer having a polymerizable unsaturated double bond used therein include fumaric acid, maleic acid, maleic anhydride, tetrahydromaleic anhydride and the like. The most preferred of these are fumaric acid, maleic acid, and 2,5-norbornene dicarboxylic acid.

The preferred weight ratio of the polymer (P) as the main chain of the present invention to the hydrophilic vinyl monomer (VM) to be grafted is in the range of P / VM = 95/5 to 40/60, It is more preferably in the range of 93/7 to 55/45, most preferably in the range of 90/10 to 60/40. When the weight ratio of the main chain polymer substance is less than 40%, the graft-polymerizable vinyl-based monomer remains without completely reacting, and properties such as heat resistance, processability, and water resistance are impaired.

Further, the weight ratio of the main chain high molecular substance is 95%.
If it is the following, the effect of improving the antibacterial property, which is the object of the present invention, will be sufficiently exhibited.

There is no great difference in the antibacterial and antifungal effects between the case where the hydrophilic substance is mixed with the polymer substance and the case where the hydrophilic substance is copolymerized.

Curing Agent In the present invention, if necessary, a curing agent capable of reacting with at least one kind of a polymer substance or a hydrophilic substance in the antibacterial / antifungal composition of the present invention is added. Is also good. By blending a curing agent, better coating film properties, for example, adhesion to automotive interior members, abrasion resistance, water resistance,
Weather resistance can be obtained.

The preferred amount of the curing agent is 5 to 35% by weight, more preferably 10 to 20% by weight, based on the total amount of the polyester resin and the hydrophilic substance. As a curing agent, an alkyl etherified amino formaldehyde resin,
Epoxy compounds and isocyanate compounds are exemplified.

The alkyl etherified aminoformaldehyde resin includes, for example, formaldehyde or paraformaldehyde alkyletherified with an alcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol and n-butanol, and urea, N , N-ethylene urea, dicyandiamide, aminotriazine and the like, and methoxylated methylol benzoguanamine, methoxylated methylol-
N, N-ethylene urea, methoxylated methylol dicyandiamide, methoxylated methylol melamine, butoxylated methylol melamine, butoxylated methylol benzoguanamine, methoxylated / butoxylated mixed type methylol melamine, etc., are preferred from the viewpoint of processability. ,
Methoxylated methylol melamine, butoxylated methylol melamine, or mixed methoxylated / butoxylated methylol melamine, each of which can be used alone or in combination.

Examples of epoxy compounds include diglycidyl ether of bisphenol A and oligomers thereof, diglycidyl ether of hydrogenated bisphenol A and oligomers thereof, diglycidyl ortho-isophthalate, diglycidyl isophthalate, diglycidyl terephthalate, and p-glycidyl ester. -Diglycidyl oxybenzoate, diglycidyl tetrahydrophthalate,
Diglycidyl hexahydrophthalate, diglycidyl succinate, diglycidyl adipate, diglycidyl sebacate, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether and polyalkylene glycol diglycidyl ethers, triglycidyl trimellitate, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylol ethane Trig of triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerol alkylene oxide adduct It can be mentioned glycidyl ethers.

Further, examples of the isocyanate compound include aromatic and aliphatic diisocyanates and tri- or higher valent polyisocyanates, and may be either low molecular weight compounds or high molecular weight compounds. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate or trimers of these isocyanate compounds, and excess of these isocyanate compounds The amount and, for example, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, low molecular active hydrogen compounds such as triethanolamine or various polyester polyols, polyether polyols, polyamides By reacting with a high molecular weight active hydrogen compound, etc. Terminal isocyanate group-containing compounds, and the like to be.

The isocyanate compound may be a blocked isocyanate. As the isocyanate blocking agent, for example, phenol, thiophenol,
Phenols such as methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol and chlorophenol, oximes such as acetoxime, methylethylketoxime and cyclohexanone oxime, alcohols such as methanol, ethanol, propanol and butanol, and ethylene chloride Phosphorus, halogen-substituted alcohols such as 1,3-dichloro-2-propanol, t-butanol, t-
Tertiary alcohols such as pentanol, ε-caprolactam, δ-valerolactam, γ-butyrolactam, β
-Lactams such as propylolactam, and other aromatic amines, imide ring, acetylacetone,
Active methylene compounds such as acetoacetate and malonic acid ethyl ester, mercaptans, imines, ureas, diaryl compounds and sodium bisulfite are also included. The blocked isocyanate can be obtained by subjecting the above isocyanate compound to an isocyanate blocking agent to undergo an addition reaction by a known appropriate method.

A known curing agent or accelerator selected according to the type of the curing agent may be used in combination with these curing agents.

The surface layer of the interior material of the automobile is composed of at least one resin selected from the group consisting mainly of urethane, polypropylene and polyester.
Isocyanate compounds are preferred from the viewpoint of coating adhesion to interior materials of such materials.

The diluting solvent for the isocyanate compound generally does not contain active hydrogen, but a secondary or tertiary alcohol having low reactivity with isocyanate groups should be added to the coating solvent of the present invention. Is possible, for example, isopropyl alcohol or t-butanol.

Antimicrobial / antifungal composition The antimicrobial / antifungal composition of the present invention may be a polymer substance to which the aforementioned antimicrobial agent component is bound alone, or a polymeric substance to which the antimicrobial agent component is bound. And, if necessary, a hydrophilic substance and a curing agent as needed, or an antibacterial agent component is combined, and a polymer substance combined with a hydrophilic substance and, if necessary, a curing agent are used as they are or diluted. It is contained in a form diluted with an agent.

As the diluent, methyl ethyl ketone,
Examples include acetone, isopropyl alcohol, t-butyl alcohol, tetrahydrofuran, dioxane, and toluene.

The antibacterial and fungicidal composition of the present invention contains calcium carbonate (C) in advance for the purpose of improving physical properties such as slipperiness, abrasion resistance, blocking resistance and concealing property of the coating film.
aCO ₃ ), calcium phosphate, apatite, barium sulfate (BaSO ₄ ), calcium fluoride (CaF ₂ ), talc, kaolin, silicon oxide (SiO ₂ ), alumina (A
l ₂ O ₃ ), titanium dioxide, zirconium oxide (Zr
Inorganic particles such as O ₂ ), iron oxide (Fe ₂ O ₃ ), and alumina / silica composite oxide, and organic materials such as polystyrene, polymethacrylate, polyacrylate, copolymers thereof, and cross-linked products thereof. It is also possible to add particles and the like.

It is also possible to add a silver-based antibacterial material such as zeolite containing silver to the antibacterial / antifungal composition of the present invention. And the addition is not preferred.

The solid content concentration of the paint is not particularly limited, but is generally about 3 to 40% by weight, preferably about 10% by weight.
The content is preferably about 30% by weight.

Automotive Interior Materials The automobile interior materials to which the present invention is applied include, for example, door trims, rear panels, pillar trims, instrument panels, armrests, headrests, and the like.
Glove boxes, console boxes, seats, floor mats, steering wheels, shift knobs, assist grips, door grips, seat buckles, rearview mirrors, sun visors, console lids, console panels, air direction adjustment for air conditioning outlets, and opening / closing door operations, etc. Knob, horn switch operation unit, ceiling material, etc.

When the interior material of the present invention is a steering wheel or a shift knob, the interior material usually comprises a hard core material and a soft coating covering the core material.・ An antifungal layer is formed. Examples of the covering member include polyurethane, polypropylene, and polyester.

The antibacterial / mildew-proof layer of the present invention comprises a polymer material having an antibacterial / mildew-proof component bonded thereto, and a hydrophilic substance, a curing agent and an inorganic Or, organic particles, etc., diluted with a diluent to paint,
It can be formed by applying this to the interior material of the automobile.

The coating thickness is not particularly limited, but is usually 5 to 50 μm, preferably 10 to 40 μm as a dry coating film.
It is. After the application, a heat treatment is carried out, in which case the temperature is usually 60 to 160 ° C, preferably 70 to 80 ° C, and the time is 1 hour.
0 to 30 minutes.

As another embodiment, the interior material may be formed by in-mold coating at the time of molding.

In another embodiment, a sheet-like member having the antibacterial / antifungal layer of the present invention as the outermost layer can be attached to the interior material. Such a sheet-like member has an adhesive layer on the back surface and the antibacterial / mold-proof layer of the present invention on the surface. Examples of the material of the sheet-like member include polyester, polyurethane, polypropylene, and a multilayer body thereof. Various known adhesives can be used as the adhesive layer. The coating thickness of the outermost layer of the sheet-shaped member is not particularly limited, but is usually 5 to 50 μm, preferably 10 to 40 μm as a dry coating film. After the application, a heat treatment is performed. In this case, the temperature is usually 60 to 160 ° C., as described above.
The time is 10 to 30 minutes. The sheet member is used by being adhered to a surface of an automobile interior material that requires antibacterial and antifungal treatment.

According to this embodiment, the antibacterial and fungicidal effects can be imparted to any existing automobile interior material very easily, and the antibacterial and fungicidal effects decrease with time. Even if it comes, it is only necessary to re-paste a new sheet-like member having an antibacterial / mold-proof layer without replacing the car interior material itself, so repair and maintenance are easy, and resources are wasted. There is an advantage that it does not become.

[0089]

Next, the present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples, but the invention is not limited to the following Production Examples and Examples.

Production Example 1 (Production of polyester resin) In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 485 parts of dimethyl terephthalate, 388 parts of dimethyl isophthalate,
161 parts of dimethyl tri-n-butyldodecylphosphonium sulfoisophthalate (hereinafter referred to as "C12 phosphonium salt"), 443.3 parts of ethylene glycol, 400.4 parts of neopentyl glycol, and tetra-n-
0.52 parts of butyl titanate was charged, and 160 to 220
The transesterification reaction was performed over 4 hours up to ° C. Next, 29 parts of fumaric acid was added, the temperature was raised to 200 to 220 ° C. over 1 hour, the pressure in the reaction system was gradually reduced, and the reaction was carried out under a reduced pressure of 0.2 mmHg for 1 hour 30 minutes to obtain a polyester.
The composition of the polyester is as shown below. Dicarboxylic acid component Terephthalic acid 50 mol% Isophthalic acid 40 mol% C12 phosphonium salt 5 mol% Fumaric acid 5 mol% Diol component Ethylene glycol 65 mol% Neopentyl glycol 35 mol%. Production Example 2 (Production of graft polymer) In a reactor equipped with a stirrer, a thermometer, a reflux device, and a fixed-rate dropping device, 300 parts of the polyester prepared in Production Example 1, 360 parts of methyl ethyl ketone, and isopropyl alcohol 12
0 parts were added and heated and stirred to dissolve the resin under reflux.
After the resin is completely dissolved, a mixture of 65 parts of acrylic acid, 35 parts of ethyl acrylate, 1.5 parts of octyl mercaptan, and a mixture of 6 parts of azobisisobutyronitrile, 90 parts of methyl ethyl ketone, and 30 parts of isopropyl alcohol Was added dropwise to the polyester solution over 1.5 hours and allowed to react for another 3 hours to obtain a graft polymer solution.

Production Example 3 (Deisotope removal of graft polymer solution)
(Ripyl alcohol) For the purpose of removing isopropyl alcohol in the graft polymer solution prepared in Production Example 2, the graft polymer solution was dropped into ion-exchanged water to insolubilize the graft polymer, and the insoluble material was dried under vacuum. A solid graft polymer was obtained. The obtained graft polymer solid was dissolved in methyl ethyl ketone to obtain a graft polymer solution.

Example 1 68.0 parts of the graft polymer solution obtained in Production Example 2
Trimethylolpropane-modified hexamethylene diisocyanate (trade name “Coronate HL”, manufactured by Nippon Polyurethane Industry Co., Ltd.) (4.0 parts) and methyl ethyl ketone (28.0 parts) were mixed to obtain a desired antibacterial and antifungal coating solution. This coating solution is applied to a urethane plate so that the applied amount of the solid content is 6.0 g / m ^2, and then heat-treated at 80 ° C. for 30 minutes to obtain an antibacterial agent.
A urethane plate laminated with a mold-resistant resin was prepared. Table 1 shows the properties of the urethane plate laminated with this antibacterial and anti-mold resin.
3 is shown.

Example 2 68.0 parts of the graft polymer solution obtained in Production Example 3
4.0 parts of trimethylolpropane-modified hexamethylene diisocyanate (trade name “Coronate HL”, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 28.0 parts of methyl ethyl ketone were mixed to obtain a desired antibacterial / antifungal coating solution. This coating solution was applied to a urethane plate so that the applied amount of the solid content was 6.0 g / m ^2, and then heat-treated at 80 ° C. for 30 minutes to prepare a urethane plate laminated with an antibacterial / antifungal resin. Table 1 shows the characteristics of the urethane plate laminated with this antibacterial and mold-resistant resin.
3 are shown.

Comparative Example 1 100.0 parts of a polyurethane solution and 1% by weight of an antibacterial and fungicidal zeolite (trade name "Zeomic", manufactured by Shinagawa Fuel Co., Ltd.) based on the solid content of polyurethane were mixed to obtain the desired antibacterial and antibacterial properties. A moldy coating solution was obtained. This coating solution was applied to a urethane plate so that the applied amount of the solid content was 6.0 g / m ^2, and then heat-treated at 80 ° C. for 30 minutes to prepare a urethane plate laminated with an antibacterial / antifungal resin. Tables 1 to 3 show the characteristics of the urethane plate on which the antibacterial / mold-resistant resin is laminated.

The antibacterial compounds obtained in Examples and Comparative Examples are described below.
The method for measuring the physical properties of the fungicidal composition will be described.

1. Antibacterial test E. coli diluted with 1/50 broth 0.1 ml of a bacterial solution (concentration: 10 ⁵ cells / ml) of Coli (Escherichia coli) is dropped on a 5 cm × 5 cm sample urethane plate which has been sterilized by high pressure steam in advance, and the sample urethane plate is sterilized by high pressure steam. The dried Saran wrap film was adhered. The sample urethane plate was transferred to a sterile petri dish and cultured at 37 ° C. for 24 hours.
Then, the bacteria on the sample urethane plate were transferred to SCDLP medium 10m.
1 and diluted 10-fold, spread on a normal agar plate, and counted the number of bacteria 24 hours later.

[0097]

(Equation 1)

The antibacterial property of the present invention means that the antibacterial rate achieves 50%, preferably 90% or more, more preferably 95% or more, and most preferably 99% or more.

2. Mold-proof test A sample urethane plate having a size of 5 cm × 5 cm was stuck on an inorganic salt agar medium plate by a method according to JIS Z 29116.2.2, and spores of the following mold 5 strains were The suspension was sprayed with 0.2 ml of a mixture obtained by adding 5% of sucrose, and
After culturing at ± 1 ° C. for 28 days, the growth state of the mold was evaluated. (Test strain) Aspergillus niger ATCC 62
75 Penicillium citrinum ATCC
9849 Chaetomium globosum ATCC
6205 Rhizopus stolonifer ATCC
10404 Aureobasidium pullulans I
FO 6353 (mold resistance display: mold resistance) 1: Mold growth is 1/3 or more of sample area 2: Mold growth is within 1/3 of sample area 3: Mold growth is not recognized.

3. Water Resistance Test The appearance of the appearance change immediately after immersion in warm water at 40 ° C. for one day was observed.

◎: No abnormality 少 し: Slight whitening Δ: Whitening ×: Elution Further, the sample urethane plate was subjected to an antibacterial test according to the method described in “1. Antibacterial test” above.

4. The state after rubbing the solvent-resistant coating film 20 times with ethyl alcohol was observed. The evaluation method is the same as in the case of water resistance.

5. Performed in accordance with the adhesion grid test method.

6. Weathering The state after irradiating the sunshine carbon weatherometer for 600 hours was observed.

◎: No abnormality ○: Light discoloration, spot Δ: Discoloration, spot ×: Severe discoloration Further, the sample urethane plate was subjected to an antibacterial test according to the method described in “1. Antibacterial test”.

7. Abrasion Resistance The state after the friction test was performed 10,000 times with a new Ford abrasion tester was observed.

◎: No abnormality ○: Slight whitening △: Fluff ×: Peeling

[0108]

[Table 1]

[0109]

[Table 2]

[0110]

[Table 3]

From the results shown in Tables 1, 2 and 3, the coating solution of Example 1 has antibacterial and antifungal properties,
Form a coating film with solvent resistance and excellent durability. In addition, no discoloration or spotting is observed, and the surface appearance is not impaired.

[0112]

As described above, according to the method of the present invention, since the interior material has a layer containing antibacterial and antifungal properties on the surface of the interior material, the interior material for automobiles that comes into direct contact with the fingers and the like is always cleaned. Can be maintained.

The antibacterial / antifungal agent of the present invention is a polymer substance having at least one of an ammonium base, a phosphonium base or a sulfonium base as an organic antibacterial material component in a molecular chain, and has high antibacterial / antifungal properties. It is maintained continuously and does not cause discoloration or spots on the interior material.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hideto Ohashi 2-1-1 Katata, Otsu-shi, Shiga Prefecture Toyobo Co., Ltd. Research Institute (72) Inventor Shigetsugu Konagaya 2-1-1 Katata, Otsu-shi, Shiga Prefecture No. 1 F-term in Toyobo Co., Ltd. Research Laboratory (Reference) 3D023 BA01 BB03 BB08 BB09 BB25 BD01 BD03 BD08 BD29 BD30 BE04 BE31 4F100 AK01C AK01K AK14C AK14J AK21C AK21J AK51 AK51H AL04C AL05BCA10 AT02 BA00 AT03 JB05C JB05K JC00 4J002 BC122 BG012 BN171 BQ002 CK031 ER006 GN00

Claims (8)

[Claims] 1. An automotive interior material mounted in an automobile interior, wherein at least a part of the surface of the polymer has at least one selected from the group consisting of an ammonium base, a phosphonium base and a sulfonium base in a molecular chain. An interior material for automobiles, comprising a layer containing a substance. 2. An interior material for an automobile to be mounted in an automobile interior, wherein a sheet-like member is attached to at least a part of a surface of the interior material, and ammonium is attached to at least a part of a surface of the sheet-like member. An automotive interior material comprising a layer containing a polymer substance having at least one selected from the group consisting of a base, a phosphonium base and a sulfonium base in a molecular chain. 3. A form in which a layer containing a polymer substance having at least one selected from the group consisting of ammonium base, phosphonium base and sulfonium base in the molecular chain is further mixed with a hydrophilic substance and the polymer substance. The automotive interior material according to claim 1, wherein the interior material comprises: 4. A layer containing a polymer having at least one selected from the group consisting of ammonium bases, phosphonium bases and sulfonium bases in the molecular chain, wherein the layer further binds a hydrophilic substance chemically to the polymer. The automotive interior material according to claim 1, wherein the interior material is contained in a form. 5. A hydrophilic substance comprising two hydrophilic groups such as a hydroxyl group, an amino group, an amide group, a carboxyl group or an alkali metal salt thereof, a sulfonic acid group or an alkali metal salt thereof, and an ether bond in one molecule. The automotive interior material according to claim 3 or 4, which is an organic compound or a polymer compound containing the above. 6. The hydrophilic substance is a vinyl polymer having a hydrophilic group in a side chain, and the vinyl polymer is obtained by graft-polymerizing the constituent monomer to the polymer substance. The automotive interior material according to claim 3 or 4, wherein: 7. A layer containing a polymer substance having at least one selected from the group consisting of an ammonium base, a phosphonium base and a sulfonium base in a molecular chain, and further comprising a layer containing a hydrophilic substance, The automotive interior material according to any one of claims 3 to 6, further comprising a curing agent capable of reacting with at least one of the conductive substances. 8. The curing agent according to claim 1, wherein the curing agent is a curing agent having an isocyanate group, and the interior material for an automobile has at least one resin selected from the group consisting of polyurethane, polypropylene and polyester as a constituent resin. The automotive interior material according to claim 7, wherein: