TWI498396B - Coating material and product of processing - Google Patents

Description

Paints and processed products

The present invention relates to an allergen reducing agent and processed articles and coatings using the same.

In Japan, it is said that one in three people suffers from allergic diseases such as atopic dermatitis, bronchial asthma, and allergic rhinitis. Examples of allergic diseases include cockroaches, pollen, mildew, and pet hair. In particular, allergens (hereinafter referred to as "sputum allergens") which account for more than 70% of the cockroaches detected in the room are problematic. It is said that the dust mites, corpses, clams, and feces of the house become allergens. Among them, allergens derived from feces are highly problematic because of their high allergen activity, and are very small and easy to fly, and are in contact with the human body, which is the most problematic.

Allergens are proteins, so they can be deactivated by modification with heat or chemical treatment (oxidizing agents, reducing agents, strong acids, strong bases). However, there is a problem that the allergen cannot be easily modified by heat or an oxidizing agent, a reducing agent, a strong acid, a strong base or the like which is safe for use in the home.

Therefore, in recent years, a method of chemically modifying the molecular surface of an allergen under relatively mild conditions has been proposed. For example, a method of modifying with an tannin (Patent Document 1), a tea extract (Patent Document 2), a hydroxybenzoic acid compound or a salt thereof (Patent Document 3), and the like, and confirming an allergen inhibitory effect have been proposed. . Further, an allergen having a compound having an aromatic hydroxy compound in a side chain of a linear polymer as an active ingredient has also been proposed. Low dose (Patent Document 4).

Prior technical literature

Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 61-44821

Patent Document 2: Japanese Patent Laid-Open No. Hei 6-279273

Patent Document 3: Japanese Patent Laid-Open No. Hei 11-292714

Patent Document 4: Japanese Patent Laid-Open Publication No. 2003-81727

However, since the compound used in the methods described in Patent Documents 1 to 3 is basically one of polyphenols, there is a problem that the coloring is brown, and if it is fixed on the surface of clothes, bedding, building materials, etc. Detrimental to design. Further, since the compound is water-soluble, there is a problem in the durability and sustainability of the allergen reducing effect when it is immobilized.

On the other hand, the allergen reducing agent described in Patent Document 4 uses a water-insoluble polymer as a linear polymer of a compound which is an active ingredient, and therefore is excellent in workability and sustainability, and is also easy. It is fixed on the surface of clothes, bedding, building materials, etc. However, the aromatic hydroxy compound of the side chain of the linear polymer is likely to be oxidatively deteriorated or hydrolyzed by heat or light, and has heat resistance (heat discoloration resistance) when applied to a member requiring high durability such as building materials. Chemical resistance is a problem. Further, since the allergen reducing agent has a high polarity of the active ingredient and the combination of the resin which is dissolved is limited, it is difficult to effectively distribute the surface to the surface, and it is difficult to easily exhibit stable allergen reducing performance. Further, even if it is dissolved, there are problems such as thickening of the coating material and poor workability. another Further, in order to synthesize a compound having an aromatic hydroxy compound in a side chain of a linear polymer, it is necessary to use a phenolic compound having at least one vinyl group as a starting material. However, phenolic compounds having at least one vinyl group are expensive and very pigmented. Therefore, when applied to a component having high design requirements such as clothes, bedding, and building materials, there is a problem that the texture of the processed product is colored.

The present invention has been made in view of the above-described facts, and an object of the present invention is to provide an allergen having a function of reducing allergens such as cockroaches or pollen, and having good heat resistance and chemical resistance, and suppressing coloration and improving workability. Reducer. Further, it is an object of the invention to provide a processed product and a coating material using the allergen reducing agent.

In order to solve the problem, the allergen reducing agent of the present invention is characterized in that a compound having a divalent molecular structure represented by the following formula (1) in the skeleton is used as an active ingredient.

In the allergen reducing agent, a compound having a divalent molecular structure represented by the formula (1) in the skeleton is preferably represented by the following formula (2), [Chemical 2]

(wherein m represents an integer of 1 or more).

In the allergen reducing agent, a compound having a structure represented by the formula (2) in the skeleton is preferably a terpene-phenol resin having a structure represented by the following formula (3) in the skeleton. a compound obtained by performing a hydrogenation reaction,

(wherein m represents an integer of 1 or more).

The processed article of the present invention is characterized in that the allergen reducing agent described above is immobilized on the surface.

The coating material of the present invention is characterized by comprising the allergen reducing agent described above and a curable resin.

Since the allergen reducing agent of the present invention contains a compound having a structure represented by the above formula (I) in the skeleton as an active ingredient, it has an allergen reducing function and is excellent in heat resistance and chemical resistance. Moreover, coloring can also be suppressed, and workability can be improved.

Since the processed product of the present invention uses the allergen reducing agent described above, it has an allergen reducing function and is excellent in heat resistance and chemical resistance. Moreover, coloring can also be suppressed.

Since the coating material of the present invention uses the allergen reducing agent described above, it has an allergen reducing function and is excellent in heat resistance and chemical resistance. Moreover, coloring can also be suppressed, and workability can be improved.

Hereinafter, the present invention will be described in detail.

The allergen reducing agent of the present invention contains, as an active ingredient, a compound having one or more exocyclohexyl groups in the skeleton, and one hydrogen atom on the ring of the cyclohexyl group is substituted with a hydroxyl group. Specifically, a compound having a divalent molecular structure of the above formula (I) in the skeleton is contained as an active ingredient. Here, the "skeleton" refers to a basic structure of a molecule, that is, a molecular skeleton structure as a main chain. Further, the "compound" is considered to be any of a polymer (polymer), an oligomer, a resin, or a condensate. The weight average molecular weight of the compound can be, for example, in the range of about 200 to 100,000.

Such a compound can be obtained, for example, by using a condensate of a phenol or a polymer or a copolymer as a raw material to hydrogenate a double bond of an aromatic ring.

Examples of the phenols include various monocyclic aromatic compounds having a hydroxyl group in an aromatic ring, or polycyclic aromatic compounds such as a polynuclear phenol or a condensed polycyclic type. Things. Specific examples thereof include the following compounds, but are not limited to these compounds.

Specific examples of the monocyclic aromatic compound include phenol, cresol, xylenol, propylphenol, and an alkyl-substituted phenol such as p-tert-butylphenol. Further, a halogenated phenol such as chlorophenol or bromophenol can be mentioned. Further, examples thereof include aromatic compounds having two or more phenolic hydroxyl groups such as resorcin, catechol, and hydroquinone. Further, methoxyphenol or the like can also be mentioned.

Specific examples of the polycyclic aromatic compound include bisphenols such as bisphenol A, bisphenol F, bisphenol AF, and bisphenol S; naphthols such as naphthol and dihydroxynaphthalene; and hydroxyindole. Further, examples of the monomer of the aromatic compound may be exemplified by formaldehyde, trioxane, cyclohexamethylenetetramine, 1,3-dioxolane or dicyclopentadiene. An aromatic polymer in which a mixture is condensed and polymerized. For example, a polycondensate of a difunctional phenol and formaldehyde can be mentioned. Examples of the difunctional phenol include those in which the ortho or para-positional hydrogen of the phenolic phenolic core such as o-cresol or p-tert-butylphenol is substituted with one other substituent, and can be used alone. Alternatively, two or more types may be used in combination.

The monomer and the polycondensate of the aromatic compound may be used alone or in combination of two or more.

Further, examples of the phenols include phenols having one or more vinyl groups. For example, vinyl phenol, tyrosine, 1,2-bis(4-hydroxyphenyl)ethylene, etc. are mentioned. These compounds may be used singly or in combination of two or more.

Examples of the phenolic polymer or copolymer include a terpene-phenol resin, an aralkyl type phenol resin, and a novolac type phenol resin. These compounds can be used in the presence of a catalyst such as an acid or a base by a known method. And manufacturing. For example, terpene - The phenol resin is obtained by reacting a cyclic terpene compound such as α-pinene, β-pinene or limonene with a phenol in the presence of a Friedel-Crafts type catalyst. The aralkyl type phenol resin is obtained by reacting a phenol with α,α'-dimethoxy-p-xylene in the presence of a keb-quasi-type catalyst. The novolac type phenol resin is obtained by reacting a phenol with formaldehyde in the presence of an acid catalyst.

In the present invention, a terpene-phenol resin is preferably used in consideration of various physical properties such as an allergen reducing function, heat resistance, chemical resistance, coloring property, and processability of the hydrogenation-reactive compound. In particular, it can be preferably used for a terpene-phenol resin having a structure represented by the above formula (3) in the skeleton, and m is preferably an integer of from 1 to 3. The terpene-phenol resin is, for example, a YS Polyster series manufactured by YASUHARA CHEMICAL CO., LTD., a Mightyace series, or the like, in the form of a commercially available product.

The compound obtained by hydrogenating a terpene-phenol resin having a structure represented by the above formula (3) in the skeleton is a compound having a structure represented by the above formula (2) in a skeleton.

The method of hydrogenation is not particularly limited, and examples thereof include hydrogenation of a noble metal such as palladium, rhodium or iridium or a noble metal or the like on a carrier such as activated carbon, activated alumina or diatomaceous earth. The method. In this case, a batch method in which the reaction is carried out while suspending the powdery catalyst may be used, or a continuous reaction method using a reaction column filled with a shaped catalyst may be employed, and the reaction form is not particularly limited.

When the raw material is a terpene-phenol resin and the reaction is in a batch mode, the amount of the catalyst used is 0.1% by weight to 50% by weight, preferably 0.2% by weight to 20% by weight based on the terpene-phenol resin. . By setting the catalyst in the range The amount can optimize the hydrogenation reaction rate and is preferred. Moreover, it is economically appropriate.

In the hydrogenation reaction, the reaction solvent may not be used, but alcohols, ethers, esters, and saturated hydrocarbons may also be used.

The reaction temperature of the hydrogenation reaction is usually from 20 ° C to 300 ° C, preferably from 50 ° C to 250 ° C. By setting the reaction temperature to 20 ° C or higher, the hydrogenation reaction rate can be further promoted, which is preferable. By setting the reaction temperature to 300 ° C or lower, it is preferred to suppress side reactions or decrease in molecular weight.

The hydrogen pressure during the hydrogenation reaction is usually about 0.5 MPa to 30 MPa. It is preferably 5 MPa to 25 MPa. More preferably, it is 8 MPa to 24 MPa. By making the hydrogen pressure 0.5 MPa or more, the hydrogenation reaction rate can be promoted, which is preferable. When the hydrogen pressure is 30 MPa or less, decomposition of the hydride can be suppressed, which is preferable.

The reaction time of the hydrogenation reaction depends on the catalyst or hydrogen pressure used and the reaction temperature, and is usually from about 0.1 to 50 hours, preferably from 0.2 to 20 hours, more preferably from 0.5 to 15 hours.

The compound having a structure represented by the above formula (1) in the skeleton may be, for example, a compound having a structure represented by the above formula (2) in the skeleton. For example, a compound represented by the following formula (4) obtained by subjecting a novolak-type phenol resin to a hydrogenation reaction, or a compound represented by the following formula (5) obtained by subjecting an aralkyl type phenol resin to hydrogenation reaction, etc. . n in the formula (4) and the formula (5) is an integer.

[Chemical 4]

The compound having the structure represented by the above formula (1) obtained in the above-mentioned skeleton is a compound having low reactivity and high stability, and has high heat resistance (heat discoloration resistance) and chemical resistance. Moreover, it can exhibit an excellent reducing effect on allergens. Examples of allergens are as follows. For example: allergens (Der1, Der2) of epidermal mites that are abundant in indoor dust, cedar pollen allergens (Cryj1, Cryj2) which are mainly floating in the air in spring, and dog dander from allergens of pets ( Canf1), cat dander (Feld1), etc. In addition, coloring can be suppressed and workability can be improved.

The allergen reducing agent of the present invention may be a compound having a structure represented by the above formula (1) in the skeleton alone, or may contain other known allergen inhibitors or hydrophilic polymers as needed without impairing the purpose. . The hydrophilic polymer is preferably a hydrophilic polymer capable of forming a reaction field which can interact with a compound having a structure represented by the above formula (1) in the skeleton. Since the allergen reducing agent contains a hydrophilic polymer, the allergen can be more effectively reduced under normal humidity conditions, for example, in an environment having an absolute humidity of 50 g/m ³ or less.

The form of use of the allergen reducing agent of the present invention is not particularly limited. For example, the allergen reducing agent can be dissolved or dispersed in a solvent to form a solution. An aqueous solvent, an oil agent, an emulsion, a suspending agent, or the like is prepared in the solution, and is immobilized on the surface of the object to be allergen-inhibited by a method such as coating or spraying to obtain a processed product. Further, examples of the solvent include water (preferably ion-exchanged water), alcohols (methanol, ethanol, propanol, etc.), hydrocarbons (toluene, xylene, methylnaphthalene, kerosene, cyclohexane, etc.), and ethers. Classes (diethyl ether, tetrahydrofuran, dioxane, etc.), esters (butyl acetate, ethyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), guanamines (N,N-dimethylformamide Wait).

Further, it is also possible to use a combination of an allergen reducing agent and a curable resin to form a curable resin composition, and to use a coating material comprising the curable resin composition.

In the case of a coating material, it is preferred that the compound having a structure represented by the above formula (1) in the skeleton contains 5 parts by weight to 20 parts by weight relative to 100 parts by weight of the coating solid content in the coating material. By setting the compound to a content within the range, the allergen-reducing effect is good, and the long-term persistence of the effect is also good. Further, in addition to economy, the physical properties of the surface of the coated article can be suppressed from being lowered.

Further, in the coating film which hardens the coating material, by having 20% by weight or less of the compound having the structure represented by the above formula (1) in the skeleton, the original function of the coating film, that is, the protective function of the surface of the substrate can be suitably obtained. Wait.

In the coating material, the curable resin contained in the curable resin composition together with the allergen reducing agent may, for example, be an active energy ray-curable resin or a thermosetting resin.

Examples of the active energy ray-curable resin include an ultraviolet curable resin and an electron beam curable resin.

Examples of the thermosetting resin include a polyester resin, a urethane resin, a melamine resin, an epoxy resin, and a silicone resin.

In the coating material, it is preferred to use an active energy ray-curable resin which can easily obtain a dense and hardened coating film having durability in a short time.

Hereinafter, a coating material comprising a curable resin composition using an active energy ray-curable resin will be described.

The coating material comprising the curable resin composition contains the above-described allergen reducing agent, and at least one selected from the group consisting of a reactive oligomer and a reactive monomer as an active energy ray-curable resin.

The reactive oligomer can be blended in a curable resin composition to improve coating film strength such as stain resistance or scratch resistance. The reactive oligomer is preferably a resin obtained by polymerizing a photocurable (meth) acrylate monomer having two or more acrylonitrile groups or methacryl oxime groups in one molecule. Examples of the reactive oligomer include (meth)acrylic acid urethane, polyester (meth) acrylate, polyether (meth) acrylate, epoxy (meth) acrylate, and polybutadiene. (Meth) acrylate, poly(oxy)oxy (meth) acrylate, and a copolymerization type (meth) acrylate in which an acryl fluorenyl group or a methacryl fluorenyl group is introduced to the side chain of the acrylate copolymer. Further, it may be a copolymer containing a unit derived from a fluorine-containing olefin, a unit derived from a polyfluorene oxide containing a polymerizable unsaturated group, or a unit derived from a hydroxyl group-containing unsaturated ether.

The above reactive oligomers may be used alone or in combination of two or more. It is preferred to use an urethane urethane having three or more acrylonitrile groups in one molecule or an epoxy acrylate having an ester modification.

The molecular weight (Mw) of the reactive oligomer is preferably in the range of 500 to 4,000. By setting the molecular weight (Mw) to 500 or more, a sufficient coating film strength can be obtained, which is preferable. When the molecular weight (Mw) is 4,000 or less, it is preferable to obtain a good balance between the viscosity of the curable resin composition, the stain resistance, and the antiallergen performance.

The amount of the reactive oligomer to be formulated is preferably from 10% by weight to 70% by weight, more preferably from 20% by weight to 50% by weight, based on the coating solids of the curable resin composition. By setting the compounding amount to 10% by weight or more, a sufficient coating film strength can be obtained, which is preferable. By setting the compounding amount to 70% by weight or less, the coating film is not too hard and is difficult to be brittle and is preferable.

The above reactive monomer can be used as a reactive diluent or a crosslinking agent. Specific examples of the reactive monomer include acrylic acid, methacrylic acid, acryloylmorpholine, N-vinylformamide, 2-ethylhexyl acrylate, lauryl acrylate, isobornyl acrylate, and acrylic acid. -3-methoxybutyl ester, ethyl carbitol acrylate, methoxy tripropylene glycol acrylate, phenoxyethyl acrylate, phenoxy polyethylene glycol acrylate, 1,4-butanediol Diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, hydroxypivalic acid neopentyl glycol acrylate, 2-(2-ethoxyethoxy)ethyl acrylate , tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, 1,3-butylene glycol diacrylate, tripropylene glycol diacrylate, 1,9-nonanediol diacrylate, 1,10-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, pentaerythritol IV Acrylate, pentaerythritol triacrylate, di-trimethylolpropane tetrapropene Acid ester, dipentaerythritol hexaacrylate, dipentaerythritol penta (hexa) acrylate, methoxy polyethylene glycol #400 acrylate, iso-cyanuric acid ethylene oxide modified diacrylate, tris(propylene oxyfluoride) Ethyl ethyl) isomeric cyanurate or the like. These compounds may be used alone or in combination of two or more.

Among the above reactive monomers, a monomer having a Tg (glass transition temperature) of 1 to 3 (meth)acrylonium groups of 100 ° C or higher can be formulated in a curable resin composition. The curable resin coating film is improved in stain resistance, scratch resistance, and crack resistance. Examples of such a monomer having a Tg of 100 ° C or higher include isobornyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, acryloyl morpholine, and tricyclodecane dimethylol di(a). Base) acrylate, iso-cyanuric acid ethylene oxide modified diacrylate, tris(propylene decyloxyethyl) isocyanurate, and the like. These compounds may be used alone or in combination of two or more.

In addition, the aliphatic hydrocarbon-based monomer having one or two (meth) acrylonitrile groups can be made to have a low viscosity of the curable resin composition without lowering the allergen reducing performance.

The allergen reducing agent has a functional group having a high hydrogen bonding ability and thus interacts with a polymer having a carbonyl group or an ether group. When a functional group having a high hydrogen bonding ability as an active site for inactivating an allergen substance interacts with a polymer due to a hydrogen bond, it may become difficult to exhibit sufficient allergen reducing performance. By using an aliphatic hydrocarbon-based monomer capable of dispersing an allergen reducing agent, the curable resin composition can be made low-viscosity without lowering the allergen reducing performance.

Examples of the aliphatic hydrocarbon-based monomer include 1,4-butanediol diacrylate. 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, hydroxypivalic acid neopentyl glycol acrylate, 1,9-nonanediol diacrylate, 1,10-nonanediol diacrylic acid Ester, glycerol triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and the like. These compounds may be used alone or in combination of two or more.

The low viscosity of the curable resin composition is achieved without lowering the allergen lowering property, and the physical properties of the other coating film are also ensured, and the amount of the reactive monomer is relative to the coating solid content of the curable resin composition. It is preferably from 3 wt% to 45 wt%, more preferably from 5 wt% to 40 wt%.

In the curable resin composition, an allergen reducing agent, a reactive oligomer, and a photopolymerization initiator other than the reactive monomer are included in the range which does not impair the effects of the present invention.

As the photopolymerization initiator, a dehydrogenation type or intramolecular split type photopolymerization initiator can be used.

Examples of the dehydrogenation type photopolymerization initiator include a benzophenone/amine system, a mazinone/benzophenone type, and a thioxanthone/amine photopolymerization initiator.

Examples of the intramolecular split type photopolymerization initiator include a benzoin type, an acetophenone type, a benzophenone type, a thioxanthone type, and a fluorenylphosphine oxide type photopolymerization initiator. Among them, preferred is a highly reactive acetophenone type 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, phenylglyoxylic acid The methyl ester has a fluorenylphosphine oxide type monodecylphosphine oxide or a bis-indenylphosphine oxide which extends to a long wavelength.

Photopolymerization from the viewpoint of improving reactivity and not impairing the physical properties of the coating film The blending amount of the initiator is preferably from 1% by weight to 10% by weight, more preferably from 3% by weight to 6% by weight, based on the coating solids of the curable resin composition.

In the curable resin composition, the above-mentioned allergen reducing agent, reactive oligomer, reactive monomer, and other additives other than the photopolymerization initiator may be blended in such a range as not to impair the effects of the present invention. Examples of such an additive include a wax, an antibacterial agent, an antifungal agent, a nonreactive diluent, a polymerization inhibitor, a matting material, an antifoaming agent, a sedimentation inhibitor, a leveling agent, a dispersing agent, a heat stabilizer, and an ultraviolet absorber. Wait.

The coating material can be obtained, for example, by dissolving a reactive oligomer, a reactive monomer, and a photopolymerization initiator in a solvent, and then adding an allergen reducing agent. When dissolved in a solvent, heating may be carried out as needed, or the above-mentioned wax, antibacterial agent, antifungal agent, non-reactive diluent, polymerization inhibitor, matting material, antifoaming agent, sedimentation inhibitor, leveling agent, Dispersing agents, heat stabilizers, ultraviolet absorbers, and the like.

As the solvent, a solvent which is usually used in paints, inks and the like can be used. Specific examples thereof include aromatic hydrocarbons such as toluene and xylene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and acetic acid such as ethyl acetate, isopropyl acetate, butyl acetate, and amyl acetate. An ester, an alcohol such as methanol, ethanol or isopropanol; an ether such as dioxane, tetrahydrofuran or diisopropyl ether; or a mixture of two or more of these compounds. Among them, a solvent having a high electron donating property such as a ketone or an acetate is more preferably dissolved.

Such a solvent can be used in the range of 30% by weight or less in the coating material. When the amount of the solvent added is in the range of 30% by weight or less, the drying proceeds smoothly, and the production rate is not greatly lowered.

The coating material thus obtained contains an allergen reducing agent containing a compound having a structure represented by the above formula (1) in the skeleton as an active ingredient. As described above, the compound has heat resistance (heat-resistant discoloration), chemical resistance, and allergen lowering function, and also suppresses coloring and improves workability, so that it has the same performance in paints.

Such a coating material is applied to the surface of a material such as a building material to suppress an allergen, and is fixed by curing, whereby a processed product having an allergen reducing function can be obtained.

In the case where the coating material is a curable resin composition containing the allergen reducing agent and the ultraviolet curable resin, the resin cured product can be used to easily ensure excellent coating film properties. The reason for this is that the compound having the structure represented by the above formula (1) in the skeleton has little absorption in the ultraviolet region of 300 nm to 240 nm, and thus it is difficult to suppress the hardening in the UV curing of the curable resin composition. On the other hand, as an active ingredient of the allergen reducing agent, the phenols used previously have a large UV absorption in an ultraviolet region of 300 nm to 240 nm. In addition, the curable resin composition containing the allergen reducing agent containing the phenol as an active ingredient and the curable resin composition of the ultraviolet curable resin is hardened by UV hardening, so that it is difficult to obtain the coating physical properties of the cured resin. Therefore, in order to ensure the physical properties of the cured film of the resin, an operation of increasing the amount of UV irradiation or a large amount of a photopolymerization initiator or the like is considered. However, there is a problem that the obtained coating film is yellowed and a good appearance cannot be obtained. . The coating of the present invention solves this problem.

Hereinafter, the present invention will be described by way of examples, but the invention is not limited thereto.

[Example]

(Example 1)

<Preparation of a hydrogenated resin compound (a compound having a structure represented by the formula (1) in the skeleton) >

It is prepared by subjecting a compound having a phenol group such as a terpene-phenol resin to a hydrogenation reaction. Specifically, 200 g of a terpene-phenol resin having a structure represented by the above formula (3) is contained in a 1 L autoclave (trade name: YS Polyster T130, YASUHARA CHEMICAL CO., LTD., hydroxy). 400 g of isopropanol was mixed with a value of 60 mgKOH/g and m=1), and 10 g of 5% rhodium/graphite catalyst was added to serve as a catalyst. The hydrogenation reaction was carried out for 15 hours under conditions of 115 ° C and 8 MPa to synthesize a hydrogenated resin compound having a structure represented by the above formula (2) in the skeleton. The hydrogenated resin compound had a weight average molecular weight of 850 and a hydroxyl value of 140 mgKOH/g.

<Modulation of Resin Coating Liquid>

30 parts by weight of the above hydrogenated resin compound was dissolved in 60 parts by weight of a diluent (butyl acetate: ethyl acetate: methyl ethyl ketone = 1:1:1) to prepare a resin coating liquid.

(Comparative Example 1)

The use of polyvinyl phenol resin MARUKA LYNCURM (manufactured by Maruzen Petrochemical Co., Ltd., has the following formula (6) in the skeleton [Chemical 5]

A resin coating liquid was prepared in the same manner as in Example 1 except that the compound of the structure (n is a positive integer) was used instead of the above-mentioned hydrogenated resin compound.

The allergen lowering performance (allergen reduction rate) and color tone of the resin coating liquid obtained in Example 1 and Comparative Example 1 were measured. The results are shown in Table 1.

Further, as Comparative Example 2, the allergen reducing performance and color tone of the unprocessed PET film to which the resin coating liquid was not applied were also measured. The results are shown together in Table 1.

<Measurement of allergen reducing performance>

1) Modulation of allergen solution

The allergen cold-dried powder (purified sputum antigen; Der2, manufactured by Asahi Breweries Co., Ltd.) was dissolved in a phosphate buffer (pH 7.6) so that the amount of allergen protein became 100 ng/ml to prepare an allergen solution.

2) Modulation of the sample

The resin coating liquids obtained in Example 1 and Comparative Example 1 were applied onto a PET film by a bar coater #20, and dried at 80 ° C for 30 minutes.

3) Implementation of the reaction

Each of the membranes prepared in the operation 2) and the unprocessed PET membrane were respectively added with 400 μl of the allergen solution prepared in the operation 1), and the allergen protein after 6 hours of reaction was measured using an ELISA kit (Indoor). the amount.

Further, the allergen reduction rate can be obtained by calculation as follows.

Allergen reduction rate (%) = 100 × (1-A / B)

A: The amount of allergen protein (ng/ml) after 6 hours of the membrane obtained in operation 2)

B: amount of allergen protein after 6 hours of unprocessed PET film (ng/ml)

<Measurement of Hue>

The color tone of the resin coating liquid was measured by Gardner's method (Comparative Example 2 is the color tone of the PET film). In addition, evaluation was performed from 0 to 18. (0 is colorless and transparent, the larger the value, the more brown)

According to the results of Table 1, it was confirmed that the processed product coated with the resin coating liquid of Example 1 (the resin coating liquid contained in the skeleton having the structure represented by the formula (1)) and coated The processed product of the resin coating liquid of Comparative Example 1 (the resin coating liquid containing the previous allergen reducing agent) also had excellent allergen reducing performance. Further, it was confirmed that the resin coating liquid of Example 1 was compared with the resin coating liquid of Comparative Example 1. The color was small, and it was less colored similarly to the PET film of Comparative Example 2 which was not coated.

(Example 2)

<Modulation of UV hardening coating>

10 parts by weight of the above-mentioned hydrogenated resin compound, 30 parts by weight of urethane acrylate (trade name: Violet 7550B, manufactured by Nippon Synthetic Chemical Co., Ltd.), and trimethylolpropane triacrylate (EO addition) (trade name: M310) 16 parts by weight of tripropylene glycol (trade name: M220, manufactured by Toagosei Chemical Co., Ltd.), 18 parts by weight, 1,9-nonanediol diacrylate (trade name: L-9CA, first industry) 18 parts by weight of methoxy diol acrylate (trade name: ME-3, manufactured by Dai-Il Pharmaceutical Co., Ltd.), 18 parts by weight of hydrophobic cerium oxide (trade name: sylophobic 702, manufactured by Fuji Silysia Co., Ltd.) 5 parts by weight, 5 parts by weight of acryl particles (trade name: GM0401S, manufactured by Ganz Chemical Co., Ltd.), and 5 parts by weight of a photopolymerization initiator (trade name: MBF, manufactured by Ciba) were stirred. , obtain UV hardening coating.

(Comparative Example 3)

In the example 2, a polyvinylphenol resin MARUKA LYNCUR M (a compound having a skeleton represented by the above formula (6) (n is an integer)) is used in place of the above hydrogenated resin compound, and Example 2 was carried out in the same manner to obtain a UV hardening coating.

(Comparative Example 4)

In the same manner as in Example 2, except that the above-mentioned hydrogenated resin compound was not blended, the UV-curable coating material was obtained.

The UV-curing coating obtained in Example 2, Comparative Example 3, and Comparative Example 4 was applied to a white olefin sheet which had been subjected to precoating treatment by a bar coater #10, and irradiated with ultraviolet rays (illuminance of 350 mJ). /cm ² ~ 400 mJ/cm ² ) and hardened to obtain a processed sheet. Then, the allergen reducing performance, color tone (coloring property), heat resistance (heat discoloration resistance), light resistance (photochromic resistance), and chemical resistance of each of the processed sheets were measured. The results are shown in Table 2.

<Measurement of allergen reducing performance>

1) Modulation of allergen solution

The allergen cold-dried powder (purified sputum antigen; Der2, manufactured by Asahi Breweries Co., Ltd.) was dissolved in a phosphate buffer (pH 7.6) so that the amount of allergen protein became 20 ng/ml to prepare an allergen solution.

2) Implementation of the reaction

The allergen solution prepared in 400 μl of the processed sheet was added dropwise to the processed sheet, and the amount of the allergen protein after the reaction for 6 hours was measured using an ELISA kit (Indoor). The allergen reduction rate can be calculated by calculation as follows.

Allergen reduction rate (%) = 100 × (1-A / B)

A: amount of allergen protein (ng/ml) after 6 hours of coating the processed sheet obtained by coating the UV hardened coating obtained in Example 2 and Comparative Example 3.

B: amount of allergen protein (ng/ml) after 6 hours of coating the processed sheet obtained by coating the UV hardened coating obtained in Comparative Example 4.

<Measurement of color tone (coloring property)>

For the color tone of the processed sheet, the color difference ⊿E was measured by a color difference meter. The evaluation criteria are as follows.

⊿E≦1: ◎

1<⊿E<2:○ (no match)

⊿E≧2:×

<Evaluation of heat resistance (heat discoloration resistance)>

The processed sheet was kept at 80 ° C for 96 hours, and after the test, the color difference ⊿ E was measured by a color difference meter. The evaluation criteria are as follows.

⊿E≦1: ◎ (no match)

1<⊿E<2:○

⊿E≧2:×

<Evaluation of light resistance (photochromism resistance)>

The processed sheet was irradiated for 48 hours by a fading test (Xe lamp), and after the test, the color difference ⊿E was measured by a color difference meter. The evaluation criteria are as follows.

⊿E≦0.5: ◎ (no match)

0.5<⊿E<1:○

⊿E≧1: × (no match)

<Evaluation of chemical resistance>

An alkaline lotion (trade name: domesto, unilever) was added to the processed sheet and kept for 24 hours to evaluate the appearance. The evaluation criteria are as follows.

No abnormal appearance: ○

Abnormal appearance (yellow): ×

According to the results of Table 2, it was confirmed that the processed sheet obtained by coating the UV hardening coating of Example 2 (the UV curable coating material containing the compound having the structure represented by the formula (1) in the skeleton) was coated with Compared with the processed product of the resin coating liquid of Comparative Example 3 (the resin coating liquid containing the prior allergen reducing agent), it has the same degree of allergen lowering property and chemical resistance, and has less coloration and heat resistance. Excellent in light and light resistance. Further, the allergen reducing performance was superior to that of the processed product coated with the resin coating liquid of Comparative Example 4.

Further, it was confirmed that the compound having the structure represented by the above formula (1) in the skeleton can be suitably used in a coating material, and it can be further applied to a resin sheet or the like and has good processability.

Claims (3)

A coating material comprising an allergen reducing agent and an ultraviolet curable resin, wherein a compound having a divalent molecular structure represented by the following formula (1) in the skeleton is an active ingredient. Here, the compound having the divalent molecular structure represented by the formula (1) in the skeleton is represented by the following formula (2). (wherein m represents an integer of 1 or more). The coating material according to the first aspect of the invention, wherein the compound having the structure represented by the formula (2) in the skeleton is a terpene having a structure represented by the following formula (3) in the skeleton - a compound obtained by hydrogenating a phenol resin, (wherein m represents an integer of 1 or more). A processed article characterized in that the coating material as described in claim 1 or 2 is immobilized on the surface.