JP2897078B2 - Resin molded article having a scratch-resistant organic hard coat layer and an anti-fogging organic hard coat layer, method for producing the same, and coating material used therefor - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a resin molded article having a scratch-resistant organic hard coat layer and an anti-fogging organic hard coat layer.

BACKGROUND ART Since resins such as polycarbonate resin, acrylic resin, transparent polyolefin resin, and polystyrene resin have excellent impact resistance and transparency, high-way sound insulation plates, automobile headlamp lenses, helmet shields, and goggles. It is used as a cover material for various devices.

However, since resin molded articles such as polycarbonate resins are hydrophobic, when the molded articles are used in a high-humidity atmosphere, dew condensation occurs on the molded article surface,
There is a disadvantage that the transparency is impaired.

Further, since a resin molded product does not have a high surface hardness like a glass product, there is also a problem that abrasion occurs on the surface of the molded product and the transparency of the molded product is impaired.

JP-A-57-69043 and JP-A-2-16185 disclose a resin molded article having a dew condensation preventing property by providing a hydrophilic polymer coating layer on the surface of the resin molded article. However, the adhesion between the hydrophilic polymer layer and the surface of the resin molded product is not sufficient, and the durability of the dew condensation preventing effect is poor.

JP-A-6-13615 discloses that a polyalkylene glycol di (meth) acrylate has a content of 0.05 to 2% by weight.
A coating agent to which a nonionic surfactant or an anionic surfactant having an HLB value of 6 to 11 has been applied is applied to the surface of a plastic molded product, and the applied surface is cured by light irradiation to form an anti-fogging organic hard coat layer. An invention for obtaining a plastic molded article having the same is disclosed. Although the plastic molded article provided with the anti-fogging organic hard coat layer produced by this method shows considerably better anti-fogging property than the conventional product, the durability of the anti-fogging effect when used in an atmosphere of high humidity is low. It is not yet satisfactory, and the abrasion resistance of this plastic molded product is insufficient, and it was used as a lighting cover for outdoor use, a sound barrier for highways, a lens for automobile headlamps, a helmet shield for motorcycles, and goggles. In such a case, there is a problem that abrasion easily occurs on the surface of these molded articles, and light transmission is reduced.

As described above, it is possible to produce a resin molded product having a certain degree of antifogging property and abrasion resistance by the conventional technology, but the antifogging property of the resin molded product rapidly increases with the lapse of use time. In addition, the antifogging property is lost and the abrasion resistance is insufficient, and there is a problem that the product has an increased amount of abrasion with time.

DISCLOSURE OF THE INVENTION The present inventors have made a resin molded article without the above-mentioned difficulties,
That is, as a result of conducting various studies for the purpose of obtaining a resin molded product having a satisfactory level of permanent scratch resistance and permanent anti-fog properties, the present invention was completed.

According to the present invention, the cross-sectional structure of the resin molded product is a novel structure, that is, a scratch-resistant organic hard coat layer having a haze value of 5% or less is provided on one surface of the substrate of the resin molded product, and a specific composition is formed on the other surface of the substrate. A resin molded article provided with an anti-fogging organic hard coat layer, which has particularly excellent adhesion between the substrate and the organic hard coat layer, and peels between the substrate and the organic hard coat layer even when bent to a radius of curvature of 50 mm or less. There is a feature that is not seen.

In the present invention, all haze values (%) are numerical values calculated by the method defined in the test item section of the resin molded product of the following examples.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an embodiment of a diagram showing a continuous production process of a polycarbonate resin plate provided with a scratch-resistant organic hard coat layer and an anti-fogging organic hard coat layer.

1: T-die 2: Sheet extruded from T-die 3: Three rolls 4: Extruded sheet 5, 7, 13, 14: Release film 6: Scratch resistant organic hard coat layer forming coating material 8: Prevention Coating material for forming cloudy organic hard coat layer 9, 12: Press roll 10, 11: First light irradiation equipment 15, 16: Second light irradiation equipment 17, 18: Resin pool of uncured coating material Implement the invention BEST MODE FOR CARRYING OUT THE INVENTION As the resin constituting the base of the resin molded article of the present invention,
Acrylic resin, polycarbonate resin, polystyrene resin, transparent polyolefin resin and the like can be mentioned, but in particular, acrylic resin and polycarbonate resin having good light transmittance are desirable, and furthermore, polycarbonate resin having good impact resistance is preferable. preferable. The thickness of the base is not particularly limited, but the thickness is considered in consideration of bending workability.
Preferably, it is in the range of 0.5 to 5 mm.

Extrusion sheets, extruded sheets,
In addition to plate-like objects such as cast sheets, lighting covers, automotive headlamp lenses, motorcycle helmet shields, goggles, and any other forms are possible. It can be made by molding.

The resin molded article of the present invention can be thermoformed into a molded article having a curved surface with a radius of curvature of 50 mm or less despite having a scratch-resistant organic hard coat layer, and furthermore, a substrate and a scratch-resistant organic hard coat layer. Are characterized by good adhesion and non-peeling.

In the case of certain motorcycle helmet goggles, an abrasion-resistant organic hard coat layer is present on the outer surface of the base (ie, the outer surface), so that it is hardly damaged by sand dust and the like, and transparency can be maintained. There is an advantage that the face (face facing the face side) is not clouded even if it is exposed to moisture such as sweat of the user.

The coating material for forming an antifogging organic hard coat layer used in the present invention has the following composition.

(A-1) 10 to 90 parts by weight of polyethylene glycol di (meth) acrylate having an average molecular weight of 150 to 2,000; (a-2) 10 to 40 parts by weight of di (meth) acrylate represented by the following general formula (1); (Wherein, R ¹ , H or CH ₃ , and m represents an integer of 2 to 50.) (a-3) At least one other copolymerizable (meth) acrylate or poly (meth) acrylate 0 A nonionic surfactant, based on 100 parts by weight of the crosslinkable polymerizable mixture (A) obtained by mixing the above (a-1) to (a-3) so that the total amount becomes 100 parts by weight; 0.1 to 15 parts by weight of a surfactant (B) comprising at least one anionic surfactant; 5 to 95 parts by weight of a monomer represented by the following general formula (2) and represented by the following general formula (3) 0.1 to 20 parts by weight of a hydrophilic copolymer (C) with 95 to 5 parts by weight of a monomer, or 10 to 150 parts by weight of metal oxide fine particles (D) chemically modified with a polymerizable silane coupling agent; Wherein R ¹ is hydrogen or CH ₃ , R ² is a C ₂ -C ₈ alkylene group, R ³ -R ⁵ is a CH ₁ -C ₅₀ alkyl group, R ⁶ is H or an alkyl group, and Z is O Alternatively, the N atom and Y represent anions of the quaternizing agent.) (Wherein, R ¹ is the same as above, A represents a C ₂ -C ₁₀ alkylene group, and n represents an integer of 1-100) and 0.01-10 parts by weight of a polymerization initiator (E). Composition.

Regarding the component (a-1) The polyalkylene glycol di (meth) acrylate having a molecular weight of 150 to 2,000 used as the component (a-1) is:
It is an essential component for forming a durable anti-fogging organic hard coat layer on the resin molded article of the present invention, and particularly, (a-
The component (1) is 15% by weight of the non-polymerizable surfactant (B) component due to a synergistic effect with the hydrophilic copolymer (C) or the metal oxide fine particles (D) chemically modified with a silane coupling agent.
It is a component which is uniformly and firmly captured in the anti-fogging organic hard coat layer in the range up to and exerts an effect to impart excellent anti-fogging property to the anti-fogging organic hard coat layer. The effect is obtained by using 10 to 90 parts by weight, particularly 50 to 90 parts by weight, of the component (a-1) in a coating material for forming an antifogging organic hard coat layer (hereinafter, simply referred to as an antifogging coating material). It becomes remarkable when there is.

The excellent trapping effect of the surfactant in the anti-fogging organic hard coat layer is not sufficient only by using the polyalkylene glycol di (meth) acrylate (a-1) as the coating material. As described in the invention, the use of a quaternary ammonium salt group-containing hydrophilic copolymer (C) or a metal oxide fine particle (D) chemically modified with a polymerizable vinyl group-containing silane coupling agent to make the composition remarkable. Can be.

(A-2) Component The alkylene glycol di (meth) acrylate represented by (a-2) has excellent film adhesion to an anti-fogging organic hard coat layer formed by the anti-fogging coating material used in the present invention. And a component that imparts scratch resistance.

The number of methylene bonds in the compound represented by formula (1) constituting (a-2) is preferably from 2 to 50, particularly preferably from 4 to 15.

Examples of the compound include ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate And the like.

The mixing amount of the component (a-2) in the antifogging coating material is 40
When the amount is in the range of parts by weight, a coating material capable of forming an anti-fogging organic hard coat layer having high scratch resistance can be obtained. However, metal oxide fine particles (D) chemically modified with a silane coupling agent can be used. When used, the antifogging organic hard coat layer having more excellent scratch resistance than the coating material can be formed without adding the component (a-2) to the antifogging coating material.

(A-3) Component As the mono- or poly (meth) acrylate represented by (a-3), methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, furfuryl (meth) acrylate , Glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, diglycerin tetra (meth)
Acrylate, dipentaerythritol hexa (meth)
Acrylate, di (meth) acrylate polyester of polyethylene oxide-modified bisphenol A, polyester poly (meth) acrylate, urethane di (meth) acrylate, and the like. This component is used to improve the viscosity and curing properties of the antifogging coating material. Preferably, it is used in an appropriate ratio of 90 parts by weight or less.

Surfactant (B) The nonionic surfactant used in the present invention is preferably a nonionic surfactant having an HLB value of 6 to 11, and particularly preferably a nonionic surfactant represented by the general formula (4). Good to use.

R ¹⁰ —O— (CH ₂ CH ₂ O) _p —H (4) (where R ¹⁰ is an alkyl group or an alkylphenyl group, p
Represents an integer of 1 to 50. Specific examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. Can be mentioned.

These nonionic surfactants are preferably used in the antifogging coating material of the present invention in a proportion of 0.1 to 15 parts by weight, especially 0.1 parts by weight of 10 parts by weight.

The anionic surfactant used in the embodiment of the present invention is represented by the general formula (5):
Specifically, phosphoric acid of polyoxyethylene derivatives such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, and polyoxyethylene nonyl phenyl ether A completely neutralized product or a partially neutralized product of mono- or diesters can be mentioned.

(Wherein, R ⁷ is an alkyl group or a phenyl group, R ⁸ is —OX or —O— (CH ₂ CH ₂ O—) _q —R ⁹ (R ⁹ is an alkyl group or a phenyl group, q is 1 to 50) X represents an alkali metal or ammonium group, and p represents an integer of 1 to 50.) The amount of the anionic surfactant added to the antifogging coating material is 0.1 to 15 parts by weight, particularly The content is preferably in the range of 0.1 to 5 parts by weight.

In order to form a better antifogging organic hard coat layer than the antifogging coating material of the present invention, a nonionic surfactant is used.
It is preferable to use 1 to 10 parts by weight together with 0.1 to 5 parts by weight of an anionic surfactant. The anti-fogging organic hard coat layer made from this coating material retains good anti-fogging property even when the wet heat history is repeated.

About the hydrophilic copolymer (C) As the hydrophilic copolymer (C), 5 to 95 parts by weight of the compound represented by the general formula (2) and 95 to 5 parts by weight of the compound represented by the general formula (3) are used. It is a copolymer, and specific examples thereof include a polymer consisting of trimethylaminopropyl methacrylamidomethyl sulfate / polyethylene glycol monomethacrylate monomethyl ether having a repeating unit 23 of 5/95 to 95/5 (weight ratio).

The amount of the hydrophilic copolymer (C) added to the anti-fog coating material is
The amount is preferably 0.1 to 50 parts by weight, particularly 0.2 to 20 parts by weight. The anti-fogging organic hard coat layer formed from the anti-fogging coating material to which the hydrophilic copolymer (C) has been added has a very low surfactant outflow from the layer and has a permanent anti-fogging property. It can be an organic hard coat layer.

Regarding Metal Oxide Fine Particles (D) The metal oxide fine particles (D) chemically modified with the polymerizable silane coupling agent used in carrying out the present invention are added to the antifogging coating material at a ratio of 0.1 to 50 parts by weight. By doing
The excellent antifogging effect of the antifogging organic hard coat layer formed from the coating material can be further enhanced, and the scratch resistance can be enhanced.

As the silane coupling agent that can be used, a compound represented by the general formula (6): (In the formula, R ¹¹ is H or CH ₃ , R ¹² , R ¹³ is H or a C ₁ -C ₁₀ alkyl group, R ¹⁴ is a C ₁ -C ₁₀ alkylene group, and s is 0-1.
And t represents an integer of 1 to 2. Or a Michael addition reaction product [I] of a primary or secondary amino group-containing silane with a polyalkylene (including those containing -O- in an alkylene bond) glycol poly (meth) acrylate, or a mercapto group-containing A Michael addition reaction product [II] of a silane and a polyalkylene (including those containing —O— in an alkylene bond) glycol poly (meth) acrylate can be given. As the polyalkylene glycol polyacrylate, a polyalkylene glycol diacrylate having a molecular weight of 150 to 1,000 is particularly preferred from the viewpoint of enhancing the effect of capturing the surfactant in the anti-fogging organic hard coat layer.

These silane coupling agents may be used in combination with a non-polymerizable silane coupling agent.

Specific examples of the silane coupling agent represented by the general formula (6) include γ- (meth) acryloyloxypropyl trialkoxysilane, di (meth) acryloyloxydialkoxysilane, and the like.

A Michael addition reaction product of a primary or secondary amino group-containing silane and a polyoxyalkylene glycol polyacrylate can be produced, for example, as follows.

Wherein R ¹⁴ is H or CH ₃ , and at least one of R ¹⁴
One H, R ¹⁵ is an alkylene group, R ¹⁶ is an alkyl group,
u represents an integer of 1 to 10, and z represents an integer of 0 to 2. The Michael addition reaction product [II] of a mercapto group-containing silane and a polyalkylene glycol poly (meth) acrylate can be produced, for example, as follows.

(In the formula, R ¹⁵ , R ¹⁶ and u are the same as above, and y represents an integer of 0 to 2.) Specific examples of the aminosilane compound include the following.

N- (2-aminoethyl-3-aminopropyl) trimethoxysilane 3-aminopropyltriethoxysilane 3-aminopropyltrimethoxysilane Specific examples of mercaptosilane include the following compounds. γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-
Mercaptopropylmethyldimethoxysilane, γ-mercaptopropylethyldimethoxysilane, γ-mercaptopropylbutyldimethoxysilane, γ-mercaptobutylmethyldimethoxysilane, γ-mercaptobutyltrimethoxysilane, γ-mercapto-2-hydroxypropyltrimethoxysilane, γ-mercapto-2-hydroxypropyltriethoxysilane, γ-mercaptopropyltriaminosilane.

Regarding the polymerization initiator (E) Further, specific examples of the metal oxide fine particles chemically modified with these silane coupling agents include particles having a particle diameter of 1 nm to 1 μm.
m, preferably 5 to 20 nm, such as titanium oxide fine particles, silicon oxide fine particles, and alumina fine particles. Examples thereof include colloidal silica and aerosil, and it is particularly preferable to use colloidal silica.

Water, methanol, as a dispersion medium of colloidal silica,
Examples include ethanol, isopropanol, butanol, cellosolve, dimethylacetoazide, toluene and xylene.

Here, the term “chemically modified with a silane coupling agent” refers to a state in which a hydrolyzate of a polymerizable silane coupling agent or a condensate thereof is held on part or all of the surface of metal oxide fine particles. This means that the surface characteristics of the metal oxide fine particles are improved.

Further, as the polymerization initiator (E) constituting the coating material for forming the anti-fogging organic hard coat layer, any known polymerization initiator can be used, and a photopolymerization initiator is particularly preferable. Benzophenone, Michler's ketone,
Benzoin butyl ether, benzoin, benzoin isopropyl ether, methyl benzoyl formate, 2
-Hydroxy-2-methyl-1-phenylpropane-1
On, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide, and the like can be given.

The amount of the polymerization initiator (E) used is (a-1) to (a-
The content is preferably in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the mixture of 3).

The coating material for forming an anti-fogging organic hard coat layer used in the present invention has the above-described structure, and is coated and cured on the surface of a resin molded product, so that it has excellent durability and anti-fogging property and scratch resistance. Sex can be given. Further, when the substrate of the resin molded product is a plate, the anti-fogging organic hard coat layer is sufficiently adhered to the resin plate without peeling even when the substrate is heated to a radius of curvature of 50 mm or less.

About the coating material for forming a scratch-resistant organic hard coat layer Next, a scratch-resistant organic hard coat layer having a haze value of 5% or less by a steel wool test provided on the other surface of the substrate of the resin molded article of the present invention is formed. In the present invention, the haze value needs to be 5% or less, preferably 3.5% or less, particularly preferably 1.5% or less.
% Or less. If the haze value exceeds 5%, when used outdoors, it is not preferable because it is scratched by dust and loses transparency.

Examples of the crosslinkable polymerizable compound [1] constituting the coating material for forming the scratch-resistant organic hard coat layer used in carrying out the present invention include, for example, an ester obtained from a polyhydric alcohol and (meth) acrylic acid or a derivative thereof. Examples of the compound include an ester compound formed from a compound, a polyhydric alcohol, a polycarboxylic acid, and (meth) acrylic acid or a derivative thereof.

As the polyhydric alcohol, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, having an average molecular weight of about 300 to
About 1000 polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, 1,4
-Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol (i.e., 2,2-dimethyl-1,3-propanediol), 2-ethylhexyl-1, Dihydric alcohols such as 3-hexanediol, 2,2'-thiodiethanol and 1,4-cyclohexanedimethanol; trimethylolpropane (ie, 1,1,1-trimethylolpropane), pentaglycerol (ie, 1,1 , 1-trimethylolethane), glycerol, 1,2,4-butanetriol, 1,
Trihydric alcohols such as 2,6-hexanetriol; and pentaerythritol (that is, 2,2-bis (hydroxymethyl) -1,3-propanediol), diglycerol, dipentaerythritol and the like.

Specific examples of the crosslinkable polymerizable compound [1] obtained as a polyhydric alcohol poly (meth) acrylate include a compound represented by the following general formula (7).

(In the formula, v is an integer of 0 to 4, X ₁ present in 4 or more molecules is a (meth) acryloyloxy group in 2 or more of them, and the remaining X _1s are each independently a hydrogen atom, Hydroxyl group,
It represents an amino group, an alkyl group or a substituted alkyl group. As the compound represented by the general formula (7), specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate,
Examples include pentaglycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol (meth) acrylate, and dipentaerythritol tetra (meth) acrylate.

Examples of the poly (meth) acrylate of a polyhydric alcohol other than the compound of the above general formula include, for example, diethylene glycol (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,4- Butanediol di (meth) acrylate, 1,6-hexanediol di (meth)
Acrylate and 1,9-nonanediol di (meth) acrylate.

When an ester compound obtained from a polyhydric alcohol and (meth) acrylic acid or a derivative thereof is used as the crosslinkable polymerizable compound [I], particularly preferred ester compounds are diethylene glycol di (meth) acrylate and triethylene glycol di (meth) acrylate. Acrylate, tetraethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane Tri (meth) acrylate, pentaglycerol acrylate and lippentaglycerol pentaacrylate.

In addition, an ester compound obtained from a polyhydric alcohol, a polycarboxylic acid, and (meth) acrylic acid or a derivative thereof, which can be used as the crosslinkable polymerizable compound [1], basically has a hydroxyl group of the polyhydric alcohol. And a mixture in which the carboxyl groups of both the polyvalent carboxylic acid and the (meth) acrylic acid or a derivative thereof finally have an equivalent amount.

Preferred among these ester compounds are polyhydric alcohols, such as dihydric alcohols, trihydric alcohols, or mixtures of dihydric alcohols and trihydric alcohols. Examples include esterified products obtained using acids. When a mixture of a trihydric alcohol and a dihydric alcohol is used, the molar ratio between the trihydric alcohol and the dihydric alcohol can be arbitrarily selected.

When a divalent carboxylic acid and (meth) acrylic acid or a derivative thereof are used in combination, the molar ratio is 2 to 1 mol of a carboxyl group of (meth) acrylic acid or a derivative thereof.
It is preferable that the carboxyl group of the polyvalent carboxylic acid be in the range of 2 mol or less.

If the divalent carboxylic acid is in excess of the above range, the viscosity of the resulting ester may be too high, making it difficult to form a coating film.

Examples of the divalent carboxylic acid or a derivative thereof used in the synthesis of the above-mentioned ester compound include aliphatic dicarboxylic acids such as succinic acid, adipic acid and sebacic acid; and fatty acids such as tetrahydrophthalic acid and 2,6-endomethylenetetrahydrophthalic acid. Aromatic dicarboxylic acids; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; and other thioglycols, thiodivalic acid, diglycolic acid, maleic acid, fumaric acid, itaconic acid, and chlorides and anhydrides thereof. As well as esters.

Specific examples of the above-mentioned ester compound used as the crosslinkable polymerizable compound [I] include malonic acid / trimethylolethane / (meth) acrylic acid, malonic acid / trimethylolpropane / (meth) acrylic acid, malonic acid / glycerin / (Meth) acrylic acid, malonic acid / pentaerythritol / (meth) acrylic acid, succinic acid / trimethylolethane / (meth) acrylic acid, succinic acid / trimethylolpropane / (meth) acrylic acid, succinic acid / glycerin / ( (Meth) acrylic acid, succinic acid / pentaerythritol / (meth) acrylic acid, adipic acid / trimethylolethane / (meth) acrylic acid, adipic acid / trimethylolpropane / (meth) acrylic acid, adipic acid / pentaerythritol / ( (Meth) acrylic acid, adipic acid /
Glycerin / (meth) acrylic acid, glutaric acid / trimethylolethane / (meth) acrylic acid, glutaric acid / trimethylolpropane / (meth) acrylic acid, glutaric acid / glycerin / (meth) acrylic acid, glutaric acid / pentaerythritol / (Meth) acrylic acid, sebacic acid / trimethylolethane / (meth) acrylic acid, sebacic acid / trimethylolpropane / (meth) acrylic acid, sebacic acid / glycerin / (meth) acrylic acid, sebacic acid / pentaerythritol / (Meth) acrylic acid, fumaric acid / trimethylolethane / (meth) acrylic acid, fumaric acid / trimethylolpropane / (meth) acrylic acid, phthalic acid / glycerin / (meth) acrylic acid, fumaric acid / pentaerythritol / ( (Meth) acrylic acid, itaconic acid / trimethic acid Ruethane / (meth) acrylic acid, itaconic acid / trimethylolpropane / (meth) acrylic acid, itaconic acid / pentaerythritol / (meth) acrylic acid, maleic anhydride / trimethylolethane / (meth) acrylic acid, or maleic anhydride Saturated or unsaturated polyester poly (meth) acrylates with acid / glycerin / (meth) acrylic acid combinations.

Further, as the crosslinkable polymerizable compound (1), for example, an isocyanate represented by the following general formula (8), (Wherein, R ¹⁷ represents an aliphatic alkylene group having 1 to 12 carbon atoms.) Hexamethylene diisocyanate, tolylene diisocyanate, diphenylethane diisocyanate, xylene diisocyanate, 4,4′-methylene bis (cyclohexyl isocyanate), isophorone diisocyanate or Polyisocyanate such as trimethylhexamethylene diisocyanate and an acrylic monomer having active hydrogen, for example, 2-hydroxyethyl ((meth) acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, N-methylol (meth) Acrylamide, N-hydroxy ((meth) acrylamide, 3-
Acryloyloxy-2-hydroxypropyl (meth)
Urethane (meth) acrylate obtained by reacting an acrylate or the like with 1 mol or more of an acrylic monomer per 1 mol of an isocyanate group by a conventional method; tris (2-hydroxyethyl) isocyanuric acid tri (meth) acrylate, etc. Poly [(meth) acryloyloxyethyl] isocyanurate is exemplified.

As the coating material for forming the scratch-resistant organic hard coat layer used in the present invention, a mixture comprising 50% by weight or more of the crosslinkable polymerizable compound [I] and 50% by weight or less of the compound [II] copolymerizable therewith was used. In this case, the haze value is 5% or less, preferably 3%.
Or less, particularly preferably 1.5% or less.

As the copolymerizable compound [II], for example, a compound having one (meth) acryloyl group in the molecule is used. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth)
Acrylate, isobutyl (meth) acrylate, t-
Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth)
Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 3,5-dimethyl-1-adamantyl (meth) acrylate, dicyclo Pentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 1,4-butylene glycol mono (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, 2-hydroxy-3-chloro Propyl (meth) acrylate,
(Meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, 2,2,2-trifluoroethyl (meth) acrylate, 2,2, 3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, N-hydroxybutyl (meth) acrylamide, hydroxymethyldiacetone (meth) acrylamide, N-hydroxyethyl-N -Methyl (meth) acrylamide.

Further, mono (meth) acrylate represented by the following general formula (9) or (10) is also included.

X ^2- (C ₂ H ₄ ) _w -R ²² (9) (Wherein, w represents 1 to 10, X ² represents a (meth) acryloyloxy group, R ²² represents an alkyl group, a substituted alkyl group,
It represents a phenyl group, a substituted phenyl group, a benzyl group or a substituted benzyl group.

Examples of the mono (meth) acrylate represented by the general formula (9) or (10) include methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and butoxyethylene Glycol (meth) acrylate.

Further, as the copolymerizable compound [II], for example, β
-(Meth) acryloyloxyethyl hydrogen phthalate, β- (meth) acryloyloxyethyl hydrogen succinate, β- (meth) acryloyloxypropyl hydrogen succinate, and various known epoxy (meth) acrylates and urethane (meth) acrylates Are also mentioned.

The compound [II] is selected according to the use of the cured film to be obtained, but if a film having a high surface hardness is desired, the compound [II]
A monomer capable of forming a homopolymer having a high glass transition temperature is used.

Specific compounds include, for example, t-butyl (meth)
Acrylate, cyclohexyl (meth) acrylate,
Examples include isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 3,5-dimethyl-1-adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and the like.

When these compounds [II] are used, they must be contained in the coating material for forming the scratch-resistant organic hard coat layer in a proportion of 50% by weight or less. The coating material can form a scratch-resistant organic hard coat layer having a haze value of 5% or less, preferably 3% or less, and more preferably 1.5% or less.

A resin sheet comprising a scratch-resistant organic hard coat layer and an anti-fogging organic hard coat layer of the present invention, wherein the resin sheet has a radius of curvature.
A particularly preferable coating material for forming a scratch-resistant organic hard coat layer which is appropriate for forming a sheet that can be bent to 50 mm or less is a divalent carboxylic acid / polyhydric alcohol / (meth) acrylic acid condensation reaction. The polyfunctional (meth) acrylate (b-) obtained by reacting 1 to 99% by weight of the obtained polyfunctional acrylate (b-1) and the isocyanate represented by the general formula (8) with a (meth) acrylate having active oxygen. 2) 20 to 80 parts by weight of a polyfunctional (meth) acrylate monomer mixture consisting of 1 to 99% by weight, urethane (meth) acrylate (b-3) 0 represented by the general formula (11)
20 parts by weight of a monomer (b-) having one or two (meth) acrylate groups and having a viscosity of 150 cp or less at 25 ° C.
4) 0.1 to 10 parts by weight of a photoinitiator (G) and 0 to 6 parts of an ultraviolet absorber (H) are added to 100 parts by weight of a crosslinkable monomer mixture (F) obtained by mixing 20 to 80 parts by weight. It is preferable to use a photocurable composition obtained by mixing. The resin molded article of the present invention, particularly a sheet, more preferably a polycarbonate sheet having a scratch-resistant organic hard coat layer formed by curing this composition can be bent without causing any inconvenience to a radius of curvature of 50 mm or less. Thus, a sheet having good workability can be obtained.

(Wherein, R ¹⁸ is hydrogen or a methyl group, R ¹⁹ is a hydrocarbon group having 1 to 8 carbon atoms, R ²⁰ is a phenylene group, a substituted phenylene group or an alkylene group having 2 to 12 carbon atoms, and R ²¹ is polycaprolactone diol. Or (A represents an integer of 1 to 8, b represents an integer of 0 to 10). The condensation mixture (b-1) is obtained by reacting a mixture such that the hydroxyl groups of the polyhydric alcohol and the carboxyl groups of both the polyhydric carboxylic acid and the (meth) acrylic acid are finally equivalent. The preferred combination in the present invention is malonic acid / trimethylolethane / (meth) acrylic acid, malonic acid / trimethylolpropane / (meth) acrylic. Acid, malonic acid / glycerin / (meth) acrylic acid, malonic acid /
Pentaerythritol / (meth) acrylic acid, succinic acid / trimethylolethane / (meth) acrylic acid, succinic acid / trimethylolpropane / (meth) acrylic acid, succinic acid / glycerin / (meth) acrylic acid, succinic acid /
Pentaerythritol / (meth) acrylic acid, adipic acid / trimethylolethane / (meth) acrylic acid, adipic acid / trimethylolethane / (meth) acrylic acid,
Adipic acid / trimethylolpropane / (meth) acrylic acid, adipic acid / glycerin / (meth) acrylic acid,
Adipic acid / pentaerythritol / (meth) acrylic acid, glutaric acid / trimethylolethane / (meth) acrylic acid, glutaric acid / trimethylolpropane / (meth) acrylic acid, glutaric acid / glycerin / (meth) acrylic acid, glutar Acid / pentaerythritol / (meth) acrylic acid, sebacic acid / trimethylolethane /
(Meth) acrylic acid, sebacic acid / trimethylolpropane / (meth) acrylic acid, sebacic acid / glycerin /
(Meth) acrylic acid, sebacic acid / pentaerythritol / (meth) acrylic acid, fumaric acid / trimethylolethane / (meth) acrylic acid, fumaric acid / trimethylolpropane / (meth) acrylic acid, fumaric acid / glycerin / ( (Meth) acrylic acid, fumaric acid / pentaerythritol / (meth) acrylic acid, itaconic acid / trimethylolethane / (meth) acrylic acid, itaconic acid / trimethylolpropane / (meth) acrylic acid, itaconic acid / glycerin / (meth) ) Acrylic acid, itaconic acid / pentaerythritol / (meth) acrylic acid, maleic anhydride / trimethylolethane / (meth) acrylic acid, maleic anhydride / trimethylolpropane / (meth) acrylic maleic anhydride / glycerin / ( (Meth) acrylic acid, maleic anhydride / pen Erythritol / (meth) acrylic acid, condensation products thereof with a combination of equal.

Preferred examples of the polyfunctional (meth) acrylate (b-2) include trimethylolpropane toluylene diisocyanate or hexamethylene diisocyanate;
An isocyanate represented by the following general formula (8) obtained by trimerization of tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), isophorodiisocyanate or trimethylhexamethylene diisocyanate; With hydrogen (meta)
Acrylic monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, N -Methylol (meth) acrylamide, N-hydroxy (meth)
Acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) acrylamide, 1,2,3-
Examples thereof include urethane (meth) acrylate obtained by reacting propanetriol-1,3 dimethacrylate, 3-acryloyloxy-2hydroxypropyl methacrylate, etc. with 3 moles or more per isocyanate molecule in a conventional manner.

Preferred examples of the urethane (meth) acrylate (b-3) represented by the general formula (11) used in the present invention include dibasic acids such as succinic acid, adipic acid and sebacic acid and ethylene glycol; -Dihydric alcohols such as butanediol and 1,6-hexanediol, hexamethylene diisocyanate, phenylene diisocyanate, 5
2 such as -methylphenylene-1,3-diisocyanate
And a combination of polycaprolactone diol and the above-mentioned divalent isocyanate.

Preferred examples of the monomer (b-4) having one or two (meth) acrylates and having a viscosity of 150 cp or less at 25 ° C. used in the present invention include methyl (meth) acrylate and ethyl (meth) acrylate. Acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth)
Acrylate, isobornyl (meth) acrylate, 2
Ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, Polyethylene glycol di (meth)
Acrylate and the like. Among them, it is particularly preferable to use 1.6-hexanediol diacrylate or 1.9-nonanediol diacrylate in terms of the balance between the adhesion of the coating film to the substrate and the scratch resistance.

Monomers (b-1) and (b-2) used in the present invention
The amount of (b-1) and (b-2) is preferably 20 to 80 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the monomer mixture (B). Resin sheet of the present invention having a scratch-resistant organic hard coat layer formed from
In particular, the polycarbonate sheet has sufficient scratch resistance,
And it can be provided with excellent thermoforming workability.

The amount of the monomer (b-1) used in the present invention is preferably 20 to 80 parts by weight based on 100 parts by weight of the monomer mixture (B), and the scratch-resistant organic hard coat layer formed from this coating material is used. The provided resin sheet of the present invention, particularly a polycarbonate sheet, has excellent scratch resistance and good thermoformability.

Further, in the present invention, the monomer (b-4) can be used in combination for the purpose of imparting flexibility of the organic hard coat layer and improving thermoformability, but the amount of the monomer (B-4) is 100 parts by weight of the monomer mixture (B). It is better to use up to 20 parts by weight.

One embodiment of a continuous production method of a polycarbonate resin plate, which is a preferred application example of a resin molded product having an antifogging property and a scratch resistance of 5% or less according to the present invention, will be described with reference to FIG. I do.

In FIG. 1, 1 is a T-die for extruding a molten polycarbonate resin into a sheet, 2 is a sheet substrate extruded from the T-die, and 3 is a three die for precisely controlling the thickness of the melt-extruded sheet substrate. Roll. The sheet substrate having passed through the three rolls is provided with a release film (polyester film) 5 having a coating material 6 for forming an abrasion-resistant organic hard coat layer on the inner surface thereof, and a coating for forming an anti-fogging organic hard coat layer. The thickness of each uncured organic hard coat layer is controlled while bonding the release film 7 having the material 8 applied on the inner surface thereof and adjusting the pressing pressure of the press roll 9. The polycarbonate resin plate coated with the uncured organic hard coat layer is then irradiated with ultraviolet light by a first light irradiation equipment consisting of 10 and 11, and the scratch-resistant organic hard coat layer and the antifogging organic hard coat are applied to both surfaces of the polycarbonate resin plate. The polycarbonate resin plate is brought into close contact with the coat layer, and then the release films 13 and 14 are peeled off from both sides of the polycarbonate resin plate through the press roller 12 to obtain the resin molded product of the present invention.

In FIG. 1, in order to further completely cure the organic hard coat layer, the organic hard coat layer is passed through the second light irradiation sections 15 and 16 and cut into a predetermined length to obtain a polycarbonate resin plate of the present invention.

17 and 18 in FIG. 1 are resin pools of the uncured coating material,
By providing the resin pool, the control of the film thickness by the press roll 9 can be efficiently performed.

At the time of the first light irradiation of the polycarbonate resin plate,
By treating the resin plate at a temperature of 30 to 70 ° C. for a certain period of time, the uncured resin swells in the range of 0.3 to 5 μm from the surface of the polycarbonate resin sheet. By performing the hardness, a polycarbonate resin plate provided with an organic hard coat layer having excellent thermoformability as well as excellent adhesiveness can be produced.

For heating the polycarbonate resin plate, heat generated from an infrared heater or an ultraviolet lamp of the first light irradiation unit can be used.

From the polycarbonate resin plate prepared as described above, the anti-fogging organic hard coat layer is on the inside, and the radius of curvature is 50 to 150 m.
In order to obtain a molded article having m, the following is preferred.

A polycarbonate resin plate is punched into a predetermined shape, for example, a shape of a motorcycle helmet shield to form a mold. Place this mold in a heating furnace at 150-200 ° C, preferably 160
Heated to ~ 170 ° C, put the heated mold into a mold, and set the radius of curvature 50 ~ with its anti-fogging organic hard coat layer inside.
A curved molded product having a diameter of 150 mm is taken out from the mold after cooling.

The polycarbonate resin plate of the present invention has excellent characteristics as a motorcycle helmet shield without the organic hard coat layer being peeled off from the polycarbonate sheet substrate at the time of punching molding, and without causing optical distortion even when subjected to bending. Have.

In the case of a lens for an automobile headlamp or the like, the substrate is first formed by an appropriate method such as injection molding, and then the surface thereof is coated with a coating material by a spraying method, a coating method or another appropriate method, and cured. It is possible.

As described above, the resin molded article of the present invention has excellent scratch resistance and antifogging properties, and has a great feature that it can be bent to a radius of curvature of 50 mm or less. In addition, it is useful as a window material for vehicles and a window material for showcases for freezing.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples.
In the examples, "parts" means parts by weight, and the test items of the resin molded product were carried out by the following methods.

[Anti-fog performance] The test piece was left standing in an atmosphere of 23 ° C and 50 RH% for 24 hours, and the temperature-controlled test piece was blown under the same conditions at a distance of 20 to 30 cm from the test piece surface to remove the cloudiness of the anti-fog hard coat surface. The occurrence state was determined based on the following criteria.

This determination was made before and after the test piece was heated under conditions of 165 ° C. × 5 minutes with the anti-fogging organic hard coat layer inside and pressed into a wooden mold having a radius of curvature of 100 mm to form a curved surface.

：: Clouding does not occur even when breath is repeatedly blown. Δ: Clouding does not occur even when breath is repeatedly blown, but the transparency of the test specimen decreases.

×: Clouding occurs when breath is repeatedly applied.

[Adhesion of Organic Hard Coat Layer] 100 squares of 1 mm × 1 mm were made on the hard coat surface of the test piece, and an adhesive tape (manufactured by Nichiban Co., Ltd.,
After attaching the cellophane tape, the operation of peeling off the adhesive tape at a stretch was repeated three times, and the number of remaining test pieces in the cross section of the organic hard coat layer was determined by n / 100.

[Scratch resistance of antifogging organic hard coat layer] After the test piece was left in a saturated steam atmosphere at 40 ° C for 5 minutes, the occurrence of scratches when the antifogging hard coat surface of the test piece was rubbed with a toe was evaluated. Judgment was made based on the following criteria.

：: No damage at all ×: Peeling occurred on the rubbed hard coat film [Formability] A 100 mm × 100 mm test piece was heated in a hot air oven at 160 ° C. for 10 minutes, and this heated sample was subjected to a radius of curvature of 15 mm. A wooden mold was pressed and bent so that the anti-fog hard coat surface was on the inside, but the state of the hard coat surface was determined according to the following criteria.

[Haze value and steel wool test] # 000 steel wool was mounted on a circular pad surface having a diameter of 25 mm, and the sample was fixed on a table of a reciprocating abrasion tester with the scratch-resistant hard coat surface facing up. With the circular pad surface in contact with the coated surface and a load of 200 g / cm ² applied,
The test piece was rotated 100 times and subjected to a wear resistance test of the sample. After washing and drying the test piece after the abrasion test, the haze value of the wear portion of the test piece was measured as a haze value with a haze meter, and the abrasion resistance of the test piece by the steel wool test was calculated by the following equation. ).

<Examples 1 to 7> The following compounds were prepared as the crosslinked polymerizable compounds (a-1), (a-2), and (a-3).

(A-1): A-200: polyethylene glycol diacrylate having an average molecular weight of 200 (manufactured by Shin-Nakamura Chemical, trade name: NK Ester A-20)
0) A-400: polyethylene glycol diacrylate having an average molecular weight of 400 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-40)
0) A-600: polyethylene glycol diacrylate having an average molecular weight of 600 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-60)
0) (a-2) C6DA: 1,6-hexanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (a-3) BPE-10: ethylene oxide 10 mol modified diphenol of bisphenol A (Daiichi Kogyo) Pharmaceutical, brand name New Frontier BPE-10) BPE-4: Diacrylate of ethylene oxide 4 mol modified bisphenol A (NK Ester A-PP, manufactured by Shin Nakamura Chemical)
E-4) TAS: trimethylolpropane / succinic acid / acrylic acid =
Condensate of 2/1/4 (molar ratio) [Nonionic surfactant] E-905: Nonionic surfactant having an HLB value of 9.2 (Kao Corporation)
A-212E: Nonionic surfactant having an HLB value of 1.3 (Plysurf A-212E, manufactured by Daiichi Pharmaceutical Co., Ltd.) E-920: Nonionic surfactant having an HLB value of 13.7 (Kao Corporation Emulgen 920) E-931: Nonionic surfactant with an HLB value of 9.2 (Kao Corporation)
Emulgen 931) [Anionic surfactant] Phosphanol LO-529 [Hydrophilic copolymer (C)] manufactured by Toho Chemical Industry Co., Ltd. In a flask with a stirrer, 88 parts of dimethylaminopropyl methacrylamide , 228 parts of methanol, 138 parts of dimethyl sulfuric acid and 41,3 parts of methanol were added dropwise with stirring while keeping the temperature inside the flask at 15 ° C or lower, and the mixture was stirred for 30 minutes after the completion of the dropwise addition to give dimethylaminopropyl methacrylamide. A quaternary solution was obtained.

3.7 parts of azobisisobutyronitrile, n-
2.4 parts of octyl mercaptan, 384 parts of methanol, 48 polyethylene glycol monomethacrylates with 23 units
5 parts were added, and polymerization was carried out at 60 ° C. under a nitrogen atmosphere for 6 hours. The obtained polymer solution was dried under vacuum at 50 ° C. for 3 hours to obtain a solid hydrophilic copolymer (C).

[Photopolymerization initiator (E)] APO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO, manufactured by BASF) [Coating material for forming scratch-resistant organic hard coat layer] Trimethylolethane / succinic acid / Acrylic acid = 2/1 /
Crosslinkable compound condensed at 4 (molar ratio) (hereinafter referred to as TAS)
Composition in which 20 parts of urethane pentaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester U-6HA: hereinafter referred to as U-6HA) and 60 parts of 1.6-hexanediol diacrylate (manufactured by Osaka Organic Chemical Industry) are mixed. As a photopolymerization initiator
A mixture of 3 parts by weight of APO and 1 part by weight of benzophenone was prepared.

<Examples 1 to 7 and Comparative Examples 1 to 6> As shown in Fig. 1, polycarbonate was melt-extruded into a sheet shape from a T-die and passed between three press rolls to obtain a polycarbonate plate having a thickness of 2 mm. On the upper surface of this polycarbonate plate, the inner surface of a polyester release film having a film thickness of 50 μm, coated with the above-mentioned coating material for forming a scratch-resistant hard coat, and bonded so that the applied surface is in contact with the polycarbonate plate surface. A coating material for forming an anti-fogging organic hard coat layer shown in Tables 1 and 2 was applied to the lower surface of a polycarbonate plate on a 50 μm-thick polyester release film surface so that the coated surface became a polycarbonate surface. And press it tightly with a press roll.
Was heated. The thickness of the coating film was 8 μm for the scratch-resistant organic hard coat layer and 12 μm for the anti-fogging organic hard coat layer.

After setting the contact time of the uncured film with the polycarbonate plate to 50 seconds, the film was passed through a metal halide lamp (ozone lens type) with an output of 120 W / cm on the upper and lower surfaces at a line speed of 1.6 m / min. Thereafter, the release film was peeled off to obtain a polycarbonate plate having the scratch-resistant organic hard coat layer and the anti-fogging organic hard coat layer of the present invention.

<Examples 8 to 14 and Comparative Examples 7 to 13> Third, the coating material for forming an anti-fogging organic hard coat layer shown in Table 4 and the coating material for forming a scratch-resistant organic hard coat layer used in Example 1 In the same manner as in Example 1, a polycarbonate plate having scratch resistance and antifogging property was prepared, and the performance was tested. Tables 3 and 4 show the results.

<Examples 15 to 17, Comparative Example 14> [Coating Material for Forming Antifogging Organic Hard Coat Layer (XV)] In a flask, 195 parts by weight of isopropanol and a polyethylene glycol diacrylate having a molecular weight of 200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 180 parts by weight of NK ester A-200), 39 parts by weight of γ-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Silicone Co., Ltd.), and 25% by weight of a 3% by weight solution of triphenylphosphine in isopropanol were sequentially added. The solution was stirred and reacted at room temperature for 3 days.

In this reaction, it was confirmed that a solution containing a polymerizable silane coupling agent obtained by a Michael addition reaction between γ-mercaptopropyltrimethoxysilane and polyethylene glycol diacrylate was obtained.

Then, while vigorously stirring a mixture of 160 parts of the obtained reaction solution and 4 parts by weight of the same type of polyethylene glycol diacrylate as used above, an isopropanol solution of colloidal silica (manufactured by Nissan Chemical Industries, Ltd. IPA
(ST: 30% by weight of solid content) 234 parts by weight, then 6 parts by weight of a 0.01 N hydrochloric acid aqueous solution were added, and the mixture was stirred at 40 ° C. for 1 hour to chemically modify colloidal silica with a silane coupling agent.

Then, a mixture of 47 parts by weight of polyethylene glycol diacrylate having a molecular weight of 400 (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-400) was added to the reaction solution, and the volatile components in the mixture were reduced under reduced pressure using a rotary evaporator. I left.

100 parts by weight of the reaction solution obtained as described above was mixed with a nonionic surfactant having an HLB value of 9.2 (manufactured by Kao Corporation, Emulgen 90).
5) 3 parts by weight, anionic surfactant of the general formula (4) (Phosphanol LO-529, manufactured by Toho Chemical Industry Co., Ltd.)
1.8 parts by weight and 1.5 parts by weight of an acylphosphine oxide as a photopolymerization initiator were added and dissolved to obtain a composition [XV] for forming an antifogging organic hard coat layer.

[Coating Material for Forming Antifogging Organic Hard Coat Layer (XVI)] In a flask, 207 parts by weight of isopropanol, 167 parts by weight of polyethylene glycol diacrylate having a molecular weight of 200 (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-200), γ -Aminopropyltrimethoxysilane (Shin-Etsu Silicone Co., Ltd.)
, KBM-903) and stirred at room temperature for 3 days.
A Michael addition reaction was performed to produce a silane compound having an acryloyloxy group and a polyethylene glycol unit.

To 82 parts by weight of the reaction solution, 52 parts by weight of the same kind of polyethylene glycol diacrylate as used above with a molecular weight of 200 was added, and while stirring vigorously, a colloidal silica isopropanol solution (manufactured by Nissan Chemical Industries, Ltd., IPA-ST) :
Add 134 parts by weight of solid content 30% by weight) and 1 part by weight of water, and add
For 1 hour to obtain a solution of silica fine particles chemically modified with a polymerizable silane coupling agent.

To this solution was added polyethylene glycol diacrylate having a molecular weight of 400 (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-40).
0) 61 parts by weight, and volatile components were distilled off under reduced pressure by a rotary evaporator.

100 parts by weight of the reaction solution obtained as described above was mixed with a nonionic surfactant having an HLB value of 9.2 (manufactured by Kao Corporation, Emulgen 90).
5) 3 parts by weight, anionic surfactant of the general formula (4) (Phosphanol LO-529, manufactured by Toho Chemical Industry Co., Ltd.)
1.8 parts by weight and 1.5 parts by weight of an acylphosphine oxide as a photopolymerization initiator were added and dissolved to obtain an antifogging organic hard coat layer-like coating material [XVI].

[Coating material for forming anti-fogging organic hard coat layer (XVII)] For forming an anti-fogging organic hard coat layer shown in Table 5 by the same method as the method for producing the coating material for forming an anti-fogging organic hard coat layer XVI. A coating [XVII] was made.

In Example 1, except that the coating materials (XV), (XVI) and (XVII) for forming an antifogging organic hard coat layer obtained as described above were used as the coating material for forming an antifogging organic hard coat layer. A polycarbonate plate having a scratch-resistant organic hard coat layer and an anti-fogging organic hard coat layer was produced in exactly the same manner.

Table 5 shows the results of examining the properties of these polycarbonate plates.

Continuation of the front page (51) Int.Cl. ⁶ identification code FI C09K 3/18 C09K 3/18 (58) Investigated field (Int.Cl. ⁶ , DB name) C08J 7/04 C09K 3/18 B32B 27 / 18 B32B 27/30 B32B 27/36

Claims (23)

(57) [Claims] An abrasion-resistant organic hard coat layer having a haze value of 5% or less is provided on one surface of a substrate, and an antifogging organic hard coat layer formed of the following coating material is provided on the other surface of the substrate. Characterized resin molded product. <Coating material for forming antifogging organic hard coat layer> (a-1) 10 to 90 parts by weight of polyethylene glycol di (meth) acrylate having an average molecular weight of 150 to 2,000; (a-2) represented by the following general formula (1) 0 to 40 parts by weight of a di (meth) acrylate to be obtained; (Wherein, R ¹ represents H or CH ₃ , and m represents an integer of 2 to 50.) (a-3) At least one of other copolymerizable (meth) acrylates and poly (meth) acrylates 0 to 90 parts by weight; Nonionic surfactant based on 100 parts by weight of the crosslinkable polymerizable mixture (A) obtained by mixing (a-1) to (a-3) so that the total amount becomes 100 parts by weight. 0.1 to 15 parts by weight of a surfactant (B) selected from anionic surfactants; and 5 to 95 parts by weight of a monomer represented by the following general formula (2) and represented by the following general formula (3) 0.1 to 20 parts by weight of a hydrophilic copolymer (C) with 95 to 5 parts by weight of a monomer, or 10 to 150 parts by weight of metal oxide fine particles (D) chemically modified with a polymerizable silane coupling agent; Wherein R ¹ is hydrogen or CH ₃ , R ² is a C ₂ -C ₈ alkylene group, R ³ -R ⁵ is a C ₁ -C ₅₀ alkyl group, R ⁶ is H or an alkyl group, and Z is O Alternatively, the N atom and Y represent anions of the quaternizing agent.) (Wherein, R ¹ is the same as above, A is an alkylene group of C _{2 to} C ₁₀ , and n is an integer of 1 to 100.) A composition containing 0.01 to 10 parts by weight of a polymerization initiator (E) . 2. A coating material for forming an anti-fogging organic hard coat layer, wherein the surfactant (B) is used in a proportion of 0.1 to 10 parts by weight of a nonionic surfactant having an HLB value of 6 to 11. The resin molded article according to claim 1, wherein 3. A surfactant (B) comprising 0.1 to 10 parts by weight of a nonionic surfactant having an HLB value of 6 to 11, and a compound represented by the general formula (5):
The resin molded article according to claim 1, wherein a coating material for forming an anti-fogging organic hard coat layer is used in combination with 0.1 to 5 parts by weight of an anionic surfactant represented by the following formula: (Wherein, R ⁷ is an alkyl group or a phenyl group, R ⁸ is —OX or —O— (CH ₂ CH ₂ O—) _q —R ⁹ (wherein R ⁹ is an alkyl group or a phenyl group, q is 1 to X represents an alkali metal or ammonium salt, and p represents an integer of 1 to 50.) 4. A Michael adduct of a polyalkylene glycol diacrylate having a molecular weight of 150 to 1000 with mercaptosilane or aminosilane as the polymerizable silane coupling agent.
The resin molded product according to any one of the above. 5. A scratch-resistant organic hard coat layer having a haze value of 5% or less is formed of a coating material for forming a scratch-resistant organic hard coat layer described below. The resin molded product according to any one of claims 1 to 7. <Scratch-resistant organic hard coat layer forming coating material> [1] Crosslinked polymerizable compound [I] having at least two (meth) acryloyloxy groups in the molecule or 50% by weight of the crosslinked polymerizable compound [I] Any one of the mixtures [II] comprising the above and 50% by weight or less of a compound copolymerizable therewith
[2] 0.01 to 10 parts by weight of a photopolymerization initiator [3] 0 to 30 parts by weight of an ultraviolet absorber [4] 0 to 5 parts by weight of a hindered amine light stabilizer 6. The resin molded article according to claim 5, wherein the resin molded article is an organic resin sheet. 7. The resin according to claim 5, wherein the substrate is a polycarbonate resin plate, an anti-fogging organic hard coat layer is formed on the inner surface thereof, and the molded product has a radius of curvature of 50 mm or less. Molding. 8. The resin molded article according to claim 7, which has a scratch-resistant organic hard coat layer comprising the following coating material for forming a scratch-resistant organic hard coat layer on the outer surface of the substrate. <Scratch-resistant organic hard coat layer forming coating material> Multifunctional (meth) acrylate monomer having two or more (meth) acryloyloxy groups in the molecule and having a viscosity at 25 ° C of 150 cp or more is 150 cp or more. (III) 20-80% by weight, a polyfunctional (meth) acrylate monomer having one or two (meth) acryloyloxy groups in the molecule and having a viscosity at 25 ° C of less than 150 cp 0.1 to 10 parts by weight of photopolymerization initiator [2], 0 to 6 parts by weight of ultraviolet absorber [3], hindered amine, based on 100 parts by weight of monomer mixture [1] consisting of 20 to 80% by weight of compound (IV) A photocurable resin composition obtained by mixing 0 to 5 parts by weight of a system light stabilizer [4]. 9. A polyfunctional acrylate (b-1) wherein the polyfunctional acrylate monomer (III) is obtained by a condensation reaction of dicarboxylic acid / polyhydric alcohol / (meth) acrylic acid.
1 to 99% by weight, and a polyfunctional (meth) acrylate (b-) obtained by reacting an isocyanate represented by the general formula (8) with a (meth) acrylate having active oxygen.
2) 1 to 99% by weight of a urethane (meth) acrylate represented by the general formula (11) The resin molded product according to claim 8, wherein the mixture is a mixture of 0 to 20 parts by weight of a related monomer (b-3). (In the formula, R ¹⁷ represents an aliphatic alkylene group having 1 to 12 carbon atoms.) (Wherein, R ¹⁸ is hydrogen or a methyl group, R ¹⁹ is a hydrocarbon group having 1 to 8 carbon atoms, R ²⁰ is a phenylene group, a substituted phenylene group or an alkylene group having 2 to 12 carbon atoms, and R ²¹ is polycaprolactone diol. Or (A represents an integer of 1 to 8, b represents an integer of 0 to 10). ) 10. The resin molded article according to claim 8, wherein the substrate is polycarbonate. 11. The resin molded article according to claim 9, wherein the substrate is a polycarbonate. 12. The polycarbonate resin plate according to claim 7, which is cut into a helmet shield shape, heated to 150 to 200 ° C., and then formed into a curved surface with a radius of curvature of 50 to 150 mm with the antifogging organic hard coat layer surface as an inner surface. A helmet shield made of polycarbonate resin. 13. A substrate of a polycarbonate resin plate is formed by a continuous extrusion molding method, and has a haze value of 5% on one surface thereof.
An uncured coating made of a scratch-resistant organic hard coat layer-forming UV-curable coating material capable of forming the following scratch-resistant organic hard coat layer, and provided on the other surface of the polycarbonate resin plate. An uncured film of the ultraviolet-curable coating material for forming an anti-fogging organic hard coat layer according to claim 3 is provided, and a light-transmitting release film is adhered to the uncured film surface to form an uncured film. A continuous method for producing a polycarbonate resin plate having an abrasion-resistant organic hard coat layer and an anti-fog organic hard coat layer, which comprises irradiating light to cure these coatings and then releasing the release film. 14. A polycarbonate resin plate having a thickness of 0.5 to 5
14. The continuous method for producing a polycarbonate resin plate according to claim 13, wherein the thickness is mm. 15. The method for continuously producing a polycarbonate resin plate according to claim 13, wherein the polycarbonate resin plate is irradiated with light while being heated to 30 to 70 ° C. 16. The method according to claim 1, wherein the swelling thickness of the polycarbonate resin plate by the coating material for forming an organic hard coat layer is 0.01 to 5 μm.
The polycarbonate resin molded product according to the above item. 17. The method according to claim 1, wherein the haze value of the scratch-resistant organic hard coat layer is 3% or less.
16. A resin molded product according to item 16. 18. The resin molded article according to claim 1, wherein the haze value of the scratch-resistant organic hard coat layer is 1.5% or less. 19. (a-1) 10 to 90 parts by weight of polyethylene glycol di (meth) acrylate having an average molecular weight of 150 to 2,000; (a-2) di (meth) acrylate 0 represented by the following general formula (1): ~ 40 parts by weight; (Wherein, R ¹ represents H or CH ₃ , and m represents an integer of 2 to 50.) (a-3) At least one of other copolymerizable (meth) acrylates and poly (meth) acrylates 0 to 90 parts by weight; Nonionic surfactant is added to 100 parts by weight of the crosslinkable polymerizable mixture (A) obtained by mixing (a-1) to (a-3) so that the total amount becomes 100 parts by weight. And 0.1 to 15 parts by weight of a surfactant (B) selected from anionic surfactants; and hydrophilicity of a monomer represented by the following general formula (2) and a monomer represented by the following general formula (3). Copolymer (C) 0.
1 to 20 parts by weight, or metal oxide fine particles (D) chemically modified with a polymerizable vinyl group-containing silane coupling agent
150 parts by weight; and Wherein R ¹ is hydrogen or CH ₃ , R ² is a C ₂ -C ₈ alkylene group, R ³ -R ⁵ is a C ₁ -C ₅₀ alkyl group, R ⁶ is H or an alkyl group, and Z is O Alternatively, the N atom and Y represent anions of the quaternizing agent.) (Wherein, R ¹ is the same as above, A represents a C ₂ -C ₁₀ alkylene group, and n represents an integer of 1 to 100.) A polymerization initiator (E) 0.01 to 10 parts by weight; Characteristic coating material for forming an anti-fogging organic hard coat layer. 20. The surfactant (B) having an HLB value of 6 to 11
20. The coating material for forming an antifogging organic hard coat layer according to claim 19, wherein the coating material for forming an antifogging organic hard coat layer used in an amount of 0.1 to 10 parts by weight of the nonionic surfactant is used. . 21. The surfactant (B) having an HLB value of 6 to 11
21. The coating for forming an anti-fogging organic hard coat layer according to claim 20, wherein 0.1 to 10 parts by weight of a nonionic surfactant and 0.1 to 5 parts by weight of an anionic surfactant represented by the general formula (5) are used in combination. Wood. (Wherein, R ⁷ is an alkyl group or a phenyl group, R ⁸ is —OX or —O— (CH ₂ CH ₂ O—) _q —R ⁹ (wherein R ⁹ is an alkyl group or a phenyl group, q is 1 to X represents an alkali metal or ammonium salt, and p represents an integer of 1 to 50.) 22. A Michael adduct of a polyalkylene glycol diacrylate having a molecular weight of 150 to 1000 and a silane containing a mercapto group or a silane containing a primary or secondary amino group as a polymerizable silane coupling agent. 22. The coating material for forming an antifogging organic hard coat layer according to any one of items 19 to 21. 23. A silane compound represented by the following general formula (12) or a general formula (13) as a polymerizable silane coupling agent:
23. The resin molded article according to claim 22, wherein a Michael addition reaction product of the compound represented by the formula (1) and poly (meth) acrylate is used. (Wherein, R ²² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ²³ is a linear or substituted alkylene group having 1 to 10 carbon atoms, and R ²⁴ and R ²⁵ are a hydrogen atom or a 1 to 10 carbon atoms. An alkylene group, a represents an integer of 0 to 2) (In the formula, R ²³ represents a linear or substituted alkylene group having 1 to 10 carbon atoms, R ²⁴ and R ²⁵ represent a hydrogen atom or an alkylene group having 1 to 10 carbon atoms, and a represents an integer of 0 to 2.)