CN112778462A - Curable composition, molded article, and laminate - Google Patents

Curable composition, molded article, and laminate Download PDF

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Publication number
CN112778462A
CN112778462A CN202011096298.2A CN202011096298A CN112778462A CN 112778462 A CN112778462 A CN 112778462A CN 202011096298 A CN202011096298 A CN 202011096298A CN 112778462 A CN112778462 A CN 112778462A
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meth
curable composition
acrylate
mass
component
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Chinese (zh)
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小高一义
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Mitsubishi Chemical Infrastructure Technology Co.,Ltd.
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Ryoko Co Ltd
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Priority claimed from JP2020139989A external-priority patent/JP7041215B2/en
Application filed by Ryoko Co Ltd filed Critical Ryoko Co Ltd
Publication of CN112778462A publication Critical patent/CN112778462A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • B32B2419/02—Bricks
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/80—Optical properties, e.g. transparency or reflexibility
    • C04B2111/82—Coloured materials

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

Provided are a curable composition which can form a cured product having excellent adhesion to a substrate and surface curability, a molded product containing the cured product, and a laminate containing the molded product. A curable composition comprising: the adhesive composition comprises a monomer A having at least 1 (meth) acryloyl group in the molecule, at least 1 compound B selected from acrylic polymers, urethane (meth) acrylates, epoxy (meth) acrylates and polyester (meth) acrylates, a polyfunctional mercapto compound C and a wax D, wherein the content of the wax D is 0.01 to 0.4 parts by mass relative to 100 parts by mass of the total amount of the monomer A and the compound B.

Description

Curable composition, molded article, and laminate
Technical Field
The invention relates to a curable composition, a molded article and a laminate.
Background
For the purpose of helping visually impaired people to move safely and comfortably, visually impaired people guidance instructions such as blind sidewalk blocks or blind sidewalk bricks are laid on the ground and floor of a platform and a sidewalk, public facilities, commercial facilities and the like of a station. Examples of the guidance instruction for the visually impaired person include a blind road block and a blind road brick having an irregular shape such as a line or a dot, and examples of the shape of the guidance instruction for the visually impaired person include a sheet shape, a block shape, a tile shape, a line shape, a dot shape, and the like.
There are various methods of applying guidance instructions to visually impaired people, and one of them is a method of applying a resin blind sidewalk sheet to a base with an adhesive to form a blind sidewalk tile. The construction method using the resin-made blind road sheet does not need to select a substrate, so that the construction is easy, and only the formed sheet needs to be pasted on the spot, so that the construction can be carried out in a short time.
The resin-made blind road sheet is produced by kneading an acrylic resin syrup with a peroxide, an aggregate, a pigment, etc. as a curing agent thereof, and then molding the kneaded mixture in a mold. As the acryl syrup, there is often used a product obtained by adding tertiary amine as a redox polymerization catalyst and dibenzoyl peroxide as a curing agent to acryl syrup in which an acryl polymer is dissolved in an acryl monomer. For example, patent document 1 describes that a resin sheet formed by using an acrylic resin paste to which a specific polyfunctional monomer is added is suitable as a blind sidewalk tile because it does not require a mold at a construction site, has excellent dimensional stability, and can be firmly adhered to a paved surface.
However, since the resin used in patent document 1 is hard, the flexibility of the resin sheet is lowered when the temperature is lowered, and if the resin sheet is attached to the base by a hard force, the elongation of the resin is insufficient, and the blind sidewalk tile after construction may be cracked. In order to solve the problem, patent document 2 discloses a curable resin composition for a blind sidewalk brick having low hardness and excellent strength and elongation, a cured product thereof, and a blind sidewalk brick using the cured product.
Documents of the prior art
[ patent document ]
[ patent document 1] Japanese patent laid-open No. 2012 and 097561
[ patent document 2] Japanese patent laid-open publication No. 2017-101407
Disclosure of Invention
Problems to be solved by the invention
However, the sheet for a blind sidewalk brick disclosed in patent document 2 is cured in a state of being covered with a PET film in order to prevent curing inhibition by oxygen, and thus, the production efficiency is low. Further, although an example is described in which wax is added in order to prevent inhibition of curing by oxygen, since a large amount of wax is used, the adhesiveness when the sheet is attached to a substrate with an adhesive tends to be low, and peeling is likely to occur.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a curable composition capable of forming a cured product having excellent adhesion to a substrate and surface curability, a molded product containing the cured product, and a laminate containing the molded product.
Means for solving the problems
The above problem can be solved by any of the following embodiments [1] to [11] of the present invention.
[1] A curable composition comprising: the adhesive composition comprises a monomer A having at least 1 (meth) acryloyl group in a molecule, at least 1 compound B selected from acrylic polymers, urethane (meth) acrylates, epoxy (meth) acrylates and polyester (meth) acrylates, a polyfunctional mercapto compound C and a wax D, wherein the content of the wax D is 0.01 to 0.4 parts by mass relative to 100 parts by mass of the total amount of the monomer A and the compound B.
[2] The curable composition according to [1], wherein the polyfunctional mercapto compound C is a polyfunctional mercapto compound having a mercapto group of at least two stages.
[3] The curable composition according to [1], wherein the polyfunctional mercapto compound C is a polyfunctional mercapto compound having 4 or more secondary or more mercapto groups.
[4] The curable composition according to any one of [1] to [3], further comprising a reducing agent E and a curing agent F.
[5] The curable composition according to any one of [1] to [4], wherein the content of the compound C is 0.05 to 2 parts by mass relative to 100 parts by mass of the total amount of the monomer A and the compound B.
[6] The curable composition according to any one of [1] to [5], wherein the curable composition is a curable composition for sidewalk tiles.
[7] A molded article comprising a cured product of the curable composition according to any one of [1] to [6 ].
[8] The shaped article according to [7], wherein the cured product contains an aggregate.
[9] The shaped article according to [7], which is a sheet for a sidewalk tile.
[10] A laminate comprising the molded article according to any one of [7] to [9] and a substrate.
[11] The laminated body according to [10], wherein the laminated body is a sidewalk tile.
Effects of the invention
According to the present invention, a curable composition capable of forming a cured product having excellent adhesion to a substrate and surface curability, a molded product containing the cured product, and a laminate containing the molded product can be provided.
Detailed Description
The embodiments of the present invention are described in detail below.
In the present invention, "(meth) acrylic acid" refers to a generic name of acrylic acid and methacrylic acid. "(meth) acrylate" refers to the generic term acrylate and methacrylate.
"(meth) acryloyl" is a generic term for both acryloyl and methacryloyl groups, and is given by the general formula: CH (CH)2(R) -C (═ O) - [ R represents a hydrogen atom or a methyl group]And (4) showing.
The curable composition of the present invention comprises: a monomer A having at least 1 (meth) acryloyl group in the molecule, a compound B of at least 1 kind selected from an acrylic polymer, urethane (meth) acrylate, epoxy (meth) acrylate and polyester (meth) acrylate, a polyfunctional mercapto compound C and a wax D. The curable composition of the present invention may further contain a reducing agent E and a curing agent F.
Hereinafter, a monomer a having at least 1 (meth) acryloyl group in the molecule, at least 1 compound B selected from an acrylic polymer, urethane (meth) acrylate, epoxy (meth) acrylate and polyester (meth) acrylate, a polyfunctional mercapto compound C, a wax D, a reducing agent E and a curing agent F are described as component a, component B, component C, component D, component E and component F, respectively, as appropriate.
[ component A ]
The component A is a monomer having at least 1 (meth) acryloyl group in the molecule.
Since the component a has a low viscosity, it has an effect of adjusting the viscosity of the curable composition to a viscosity suitable for molding. The component A also has the effect of adjusting the hardness of the cured product.
Specific examples of the component A include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, and stearyl (meth) acrylate; alicyclic structure-containing (meth) acrylic monomers such as cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and adamantyl (meth) acrylate; (meth) acrylic monomers having an aromatic ring structure such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, phenyl (meth) acrylate, phenylphenoxyethyl (meth) acrylate, phenoxybenzyl (meth) acrylate, phenylbenzyl (meth) acrylate, naphthyl (meth) acrylate, and (1-naphthyl) meth (meth) acrylate; alkoxy (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and butoxyethyl (meth) acrylate; (meth) acrylic acid monomers having a heterocyclic structure such as tetrahydrofuran (meth) acrylate and glycidyl (meth) acrylate; other (meth) acrylates such as 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 2- (meth) acryloyloxyethyl phosphate, trifluoroethyl (meth) acrylate, perfluorodecyl (meth) acrylate, and (meth) acryloylmorpholine; other vinyl group-containing monomers such as styrene, α -methylstyrene, acrylonitrile, and vinyl acetate; alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and 1, 3-butylene glycol di (meth) acrylate; 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, or the like; polyalkylene glycol di (meth) acrylates such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, dibutylene glycol di (meth) acrylate, tributylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polybutylene glycol di (meth) acrylate; alkoxylated bisphenol a di (meth) acrylates such as bisphenol a ethylene oxide adduct di (meth) acrylate and bisphenol a propylene oxide adduct di (meth) acrylate; tricyclodecane dimethanol di (meth) acrylate; difunctional (meth) acrylates such as polycarbonate diol di (meth) acrylate; trifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, and epsilon-caprolactone-modified tri ((meth) acryloyloxyethyl) isocyanurate; tetrafunctional (meth) acrylates such as di-trimethylolpropane tetra (meth) acrylate; pentafunctional (meth) acrylates such as dipentaerythritol penta (meth) acrylate; and hexafunctional (meth) acrylates such as dipentaerythritol hexa (meth) acrylate. These components A may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Among them, the component a is preferably a monomer having 1 (meth) acryloyl group in 1 molecule from the viewpoint of dilutability. The component A preferably contains methyl (meth) acrylate from the viewpoint of high hardness of a cured product of the curable composition, and preferably contains alkyl (meth) acrylate having 3 to 10 carbon atoms and an alkyl group from the viewpoint of high elongation of the cured product, and more preferably contains at least one or both of n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate.
The curable composition preferably contains both methyl (meth) acrylate and alkyl (meth) acrylate having an alkyl group with 3 to 10 carbon atoms, from the viewpoint of achieving a balanced hardness and elongation of a cured product of the curable composition. The ratio (mass ratio) of methyl (meth) acrylate to alkyl (meth) acrylate having an alkyl group with 3 to 10 carbon atoms is preferably 80/20 to 20/80, and more preferably 70/30 to 30/70.
From the viewpoint of improving the production efficiency of a cured product by shortening the gelation time of the curable composition and improving the strength of the cured product, the curable composition preferably contains a polyfunctional (meth) acrylate having at least 2 (meth) acryloyl groups in the molecule. The polyfunctional (meth) acrylate is preferably a difunctional (meth) acrylate having 2 (meth) acryloyl groups in the molecule, and examples thereof include the difunctional (meth) acrylates described above. Among them, polyalkylene glycol di (meth) acrylate and alkoxylated bisphenol a di (meth) acrylate are preferable from the viewpoint of giving a cured product having high strength and high elongation.
The content of the polyfunctional (meth) acrylate in the curable composition is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less, based on 100 parts by mass of the total amount of the components a and B, from the viewpoint of providing a cured product with high elongation. The content of the polyfunctional (meth) acrylate in the curable composition is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and still more preferably 1 part by mass or more, based on 100 parts by mass of the total amount of the components a and B, from the viewpoint of obtaining a sufficient addition effect (shortening of the gelation time and improvement of the strength of the cured product).
The content of the component a in the curable composition is preferably 50 to 95 parts by mass, more preferably 60 to 90 parts by mass, based on 100 parts by mass of the total amount of the components a and B. When the content of the component a is within the above range, the curable composition easily flows into a mold.
[ component B ]
The component B is at least 1 compound selected from acrylic polymers, urethane (meth) acrylates, epoxy (meth) acrylates and polyester (meth) acrylates.
The component B has an effect of increasing the elongation of a cured product of the curable composition. The component B also has the effect of relaxing shrinkage during curing and improving the dimensional accuracy of the cured product.
(acrylic Polymer)
As the acrylic polymer of the component B, those obtainable by radical polymerization of an acrylic monomer can be used.
Specific examples of the acrylic monomer include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, and stearyl (meth) acrylate; alicyclic structure-containing (meth) acrylic monomers such as cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and adamantyl (meth) acrylate; (meth) acrylic monomers having an aromatic ring structure such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, phenyl (meth) acrylate, phenylphenoxyethyl (meth) acrylate, phenoxybenzyl (meth) acrylate, phenylbenzyl (meth) acrylate, naphthyl (meth) acrylate, and (1-naphthyl) meth (meth) acrylate; alkoxy (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and butoxyethyl (meth) acrylate; (meth) acrylic acid monomers having a heterocyclic structure such as tetrahydrofuran (meth) acrylate and glycidyl (meth) acrylate; other (meth) acrylates such as 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 2- (meth) acryloyloxyethyl phosphate, trifluoroethyl (meth) acrylate, perfluorodecyl (meth) acrylate, and (meth) acryloylmorpholine; and other vinyl group-containing monomers such as styrene, α -methylstyrene, acrylonitrile, and vinyl acetate. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The acrylic monomer forming the acrylic polymer of component B is preferably methyl methacrylate from the viewpoint of giving a cured product of the curable composition high strength, and is preferably an alkyl (meth) acrylate having an alkyl group with 3 to 10 carbon atoms from the viewpoint of giving a cured product of the curable composition high elongation.
The content of the methyl methacrylate unit (b-1) in the acrylic polymer is preferably 20 to 95% by mass, more preferably 40 to 95% by mass, and still more preferably 40 to 70% by mass. The higher the content of the unit (b-1) in the acrylic polymer is, the higher the hardness of the cured product can be.
The content of the alkyl (meth) acrylate unit (b-2) having an alkyl group with 3 to 10 carbon atoms in the acrylic polymer is preferably 5 to 80% by mass, more preferably 5 to 60% by mass, and still more preferably 30 to 60% by mass. The higher the content of the unit (b-2) in the acrylic polymer, the higher the elongation of the cured product.
The content of the monomer unit (b-3) other than the unit (b-1) and the unit (b-2) is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and still more preferably 0 to 5% by mass. The monomer unit (b-3) can adjust the properties of the cured product such as strength, elongation, and hardness, but if the monomer unit (b-3) is too large, the hardness and elongation of the cured product may be reduced.
The weight average molecular weight of the acrylic polymer is not particularly limited, but is preferably 1000 to 300000, more preferably 5000 to 200000, and further preferably 10000 to 150000. When the weight average molecular weight is within the above range, the viscosity of the curable composition is low, and therefore the curable composition easily flows into a mold, and the moldability of the curable composition is improved. The weight average molecular weight is a value in terms of polystyrene, which is a molecular weight measured by dissolving a polymer in a solvent (tetrahydrofuran) and using gel permeation chromatography (hereinafter, referred to as "GPC"). The details of the measurement will be described later.
The glass transition temperature of the acrylic polymer is not particularly limited, but is preferably 30 to 100 ℃, more preferably 35 to 90 ℃, and still more preferably 40 to 80 ℃. The higher the glass transition temperature is in the above range, the more the strength of the cured product of the curable composition can be improved. The lower the glass transition temperature is in the above range, the lower the hardness and the higher the elongation of the cured product of the curable composition can be.
The polymerization method for obtaining the acrylic polymer is not particularly limited, and polymerization can be carried out by a known method such as solution polymerization, suspension polymerization, emulsion polymerization, partial polymerization, and the like. In the present invention, the suspension polymerization method is preferred because the control of the polymerization reaction and the separation of the polymer to be produced are relatively easy.
(urethane (meth) acrylate)
Examples of the urethane (meth) acrylate as the component B include compounds obtained by addition reaction of a polyisocyanate, a polyol and a hydroxyl group-containing (meth) acrylate. The urethane (meth) acrylate as the component B includes a compound obtained by addition reaction of a polyisocyanate and a hydroxyl group-containing (meth) acrylate without using a polyol.
Specific examples of the polyisocyanate include aromatic isocyanates such as Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and Naphthalene Diisocyanate (NDI); aliphatic isocyanates such as isophorone diisocyanate (IPDI) and Hexamethylene Diisocyanate (HDI). Further, triisocyanate compounds such as biuret modified products and urea modified products of isophorone diisocyanate and hexamethylene diisocyanate; mixtures of polyisocyanate compounds having a valence of 3 or more, such as polymethylene polyphenyl isocyanate. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Specific examples of the polyol include polyether polyols such as polytetramethylene ether glycol, polyester polyols such as a reaction product of adipic acid and propylene glycol, polycaprolactone polyols, polycarbonate polyols, and polyacrylate polyols. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The weight average molecular weight of the polyol is preferably 400 or more from the viewpoint of making a cured product of the curable composition have high elongation, and is preferably 10000 or less from the viewpoint of making a cured product of the curable composition have high strength. The weight average molecular weight of the polyol is more preferably 1000 or more, and still more preferably 3000 or less.
Specific examples of the hydroxyl group-containing (meth) acrylate include (meth) acrylates having a hydroxyalkyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; a gamma-butyrolactone ring-opening adduct or an epsilon-caprolactone ring-opening adduct to 2-hydroxyethyl (meth) acrylate; a ring-opening adduct of ethylene oxide or a ring-opening adduct of propylene oxide to (meth) acrylic acid; (meth) acrylates having a hydroxyl group at the end, such as dimers and trimers of 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and the like. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The hydroxyl group-containing (meth) acrylate is preferably 2-hydroxyethyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate from the viewpoint of compatibility with other components in the curable composition and various physical properties.
The weight average molecular weight of the urethane (meth) acrylate is preferably 1000 or more, and more preferably 5000 or more, from the viewpoint of high elongation of a cured product of the curable composition due to an appropriate crosslinking point pitch. The weight average molecular weight of the urethane (meth) acrylate is preferably 50000 or less from the viewpoint of reducing the viscosity of the curable composition and facilitating flow into a mold. The weight average molecular weight of the urethane (meth) acrylate is more preferably 5000 or more, and still more preferably 20000 or less.
In the synthesis of urethane (meth) acrylate, the polyisocyanate/polyol and the hydroxyl group-containing (meth) acrylate are preferably used in a ratio of 1/1 in terms of the molar ratio of functional groups (NCO/OH).
The method for synthesizing the urethane (meth) acrylate is not particularly limited. For example, a method in which a catalyst (di-n-butyltin dilaurate or the like) is added to a polyisocyanate, and a polyol and a hydroxyl group-containing (meth) acrylate are sequentially added dropwise while maintaining the temperature at 40 to 80 ℃.
(epoxy (meth) acrylate)
The epoxy (meth) acrylate as the component B is preferably a compound obtained by reacting a partially esterified product of a polybasic acid anhydride and a hydroxyl group-containing (meth) acrylate, a difunctional bisphenol A type epoxy resin and an unsaturated monobasic acid by a known method.
As the bifunctional bisphenol a type epoxy resin, a general-purpose epoxy resin obtained by reacting bisphenol a with epichlorohydrin can be used.
Examples of the polybasic acid anhydride include anhydrides of phthalic acid, isophthalic acid, tetrahydrophthalic acid, succinic acid, maleic acid, fumaric acid, adipic acid, and the like. Examples of the hydroxyl group-containing (meth) acrylate include compounds exemplified as hydroxyl group-containing (meth) acrylates that can be used for forming the urethane (meth) acrylate.
Examples of the unsaturated monobasic acid include (meth) acrylic acid and the like.
(polyester (meth) acrylate)
The polyester (meth) acrylate as the component B is preferably a compound obtained by reacting a polybasic acid or an acid anhydride thereof, a polyhydric alcohol compound, (meth) acrylic acid or glycidyl (meth) acrylate by a known method.
Examples of the polybasic acid include phthalic acid, isophthalic acid, tetrahydrophthalic acid, succinic acid, maleic acid, fumaric acid, and adipic acid, and examples of the polybasic acid anhydride include anhydrides of these polybasic acids. Examples of the polyhydric alcohol include ethylene glycol and propylene glycol.
(content of component B)
The content of the component B in the curable composition is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the total amount of the components A and B. When the content of the component B is within the above range, the dimensional stability of the molded article becomes good.
[ component C ]
The component C is a polyfunctional mercapto compound and has an effect of improving the curability of the curable composition.
The polyfunctional mercapto compound is not particularly limited as long as it has 2 or more mercapto groups in 1 molecule, but an aliphatic mercapto compound is preferable. As the component C, a mercapto compound having a primary mercapto group, a mercapto compound having a secondary mercapto group, and a mercapto compound having a tertiary mercapto group can be used. Among these, from the viewpoint of improving curability, a polyfunctional mercapto compound having a primary or secondary mercapto group having 2 mercapto groups is preferable, a polyfunctional mercapto compound having a primary or secondary mercapto group having 3 mercapto groups is more preferable, and a polyfunctional mercapto compound having a primary or secondary mercapto group having 4 or more mercapto groups is further preferable. In addition, the component C is preferably a polyfunctional mercapto compound having a mercapto group of two or more stages from the viewpoint of storage stability of the curable composition.
Specific examples of the polyfunctional mercapto compound having a primary (primary) mercapto group include difunctional mercapto compounds such as tetraethyleneglycol dimercaptoacetate and tetraethyleneglycol bis (3-mercaptopropionate); trifunctional mercapto compounds such as trimethylolethane tris (3-mercaptopropionate), trimethylolpropane trimercaptoacetate, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (4-mercaptobutyrate), tris- [ (3-mercaptopropionyloxy) -ethyl ] -isocyanurate, tris- [ (3-mercaptobutyryloxy) -ethyl ] -isocyanurate, glycerol tris- (3-mercaptopropionate), and glycerol tris- (4-mercaptobutyrate); tetrafunctional mercapto compounds such as pentaerythritol tetramercaptoacetate, pentaerythritol tetrakis (3-mercaptopropionate), and pentaerythritol tetrakis (4-mercaptobutyrate); and polyfunctional mercapto compounds having more than four functions, such as dipentaerythritol hexametaphosphate, dipentaerythritol hexa (3-mercaptopropionate), and dipentaerythritol hexa (4-mercaptobutyrate).
Specific examples of the polyfunctional mercapto compound having a secondary (secondary) mercapto group include ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), tetraethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), ethylene glycol bis (4-mercaptovalerate), diethylene glycol bis (4-mercaptovalerate), butanediol bis (4-mercaptovalerate), Octanediol bis (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), propylene glycol bis (3-mercaptovalerate), diethylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate), octanediol bis (3-mercaptovalerate), hydrogenated bisphenol A bis (3-mercaptobutyrate), difunctional mercapto compounds such as bisphenol a dihydroxyethyl ether-3-mercaptobutyrate, ethylene glycol bis (3-mercapto-3-phenylpropionate), propylene glycol bis (3-mercapto-3-phenylpropionate), diethylene glycol bis (3-mercapto-3-phenylpropionate), butanediol bis (3-mercapto-3-phenylpropionate), and octanediol bis (3-mercapto-3-phenylpropionate); trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (2-mercaptopropionate), 1, 4-bis (3-mercaptobutanoyloxy) butane, 1,3, 5-tris [2- (3-mercaptobutanoyloxyethyl) ] -1, 3, 5-triazine-2, 4, 6(1H, 3H, 5H) -trione, trifunctional mercapto compounds such as trimethylolpropane tris (4-mercaptovalerate), tris- [ (3-mercaptobutanoyloxy) -ethyl ] -isocyanurate, trimethylolpropane tris (3-mercaptovalerate), trimethylolpropane tris (3-mercapto-3-phenylpropionate), and tris-2- (3-mercapto-3-phenylpropionate) ethyl isocyanurate; tetrafunctional mercapto compounds such as pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (2-mercaptopropionate), pentaerythritol tetrakis (4-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate), and pentaerythritol tetrakis (3-mercapto-3-phenylpropionate); and polyfunctional mercapto compounds having more than four functional groups such as dipentaerythritol hexa (3-mercaptobutyrate), dipentaerythritol hexa (2-mercaptopropionate), dipentaerythritol hexa (4-mercaptovalerate), dipentaerythritol hexa (3-mercaptovalerate), and dipentaerythritol hexa (3-mercapto-3-phenylpropionate).
Specific examples of the polyfunctional mercapto compound having a tertiary (tertiary) mercapto group include bis (2-mercaptoisobutyl) phthalate, ethylene glycol bis (2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate), bis (3-mercapto-3-methylbutyl) phthalate, ethylene glycol bis (3-mercapto-3-methylbutyrate), propylene glycol bis (3-mercapto-3-methylbutyrate), diethylene glycol bis (3-mercapto-3-methylbutyrate), butanediol bis (3-mercapto-3-methylbutyrate), and the like, Difunctional mercapto compounds such as octanediol bis (3-mercapto-3-methylbutyrate); trifunctional mercapto compounds such as trimethylolethane tris (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), trimethylolethane tris (3-mercapto-3-methylbutyrate), and trimethylolpropane tris (3-mercapto-3-methylbutyrate); tetrafunctional mercapto compounds such as pentaerythritol tetrakis (2-mercaptoisobutyrate) and pentaerythritol tetrakis (3-mercapto-3-methylbutyrate); and polyfunctional mercapto compounds having more than four functions, such as dipentaerythritol hexa (2-mercaptoisobutyrate) and dipentaerythritol hexa (3-mercapto-3-methylbutyrate).
The component C may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The content of the component C is preferably 0.05 to 2 parts by mass, more preferably 0.1 to 1.5 parts by mass, based on 100 parts by mass of the total amount of the components A and B. When the amount of the component C in the polyfunctional mercapto compound is larger than the above range, the curability of the curable composition tends to be improved.
On the other hand, since the polyfunctional mercapto group is relatively expensive, the less the amount of addition thereof falls within the above range, the more economical the curable composition tends to be.
[ component D ]
The component D is a wax and has an effect of improving the surface curability of the curable composition.
The component D floats on the surface of the curable composition to form a film, thereby suppressing contact between oxygen in the air and the components A and B, and improving the surface curability of the curable composition. The larger the content of the component D, the more the surface curability tends to be improved.
On the other hand, when a laminate is formed using the curable composition, component D formed on the surface of a cured product of the curable composition tends to reduce the adhesion to an adjacent layer. For example, when a sheet for a blind sidewalk brick obtained by curing and molding the curable composition with an adhesive is stuck to a concrete substrate, the component D tends to reduce the adhesiveness at the interface between the sheet for a blind sidewalk brick and the adhesive.
In the curable composition of the present invention, the content of the component D is 0.01 to 0.4 parts by mass relative to 100 parts by mass of the total amount of the components a and B from the viewpoint of the surface curability and the adhesiveness.
The content of the component D is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and further preferably 0.2 parts by mass or more, based on 100 parts by mass of the total amount of the components a and B, from the viewpoint of enhancing the surface curability of the curable composition. When the content of the component D is less than 0.01 part by mass relative to 100 parts by mass of the total of the components A and B, the surface curability is lowered.
On the other hand, the content of the component D is preferably 0.35 parts by mass or less, more preferably 0.3 parts by mass or less, relative to 100 parts by mass of the total amount of the components a and B, from the viewpoint of the adhesiveness between the cured product of the curable composition and the contact layer in the laminate. If the content of the component D is more than 0.4 parts by mass relative to 100 parts by mass of the total amount of the components a and B, the adhesiveness between the cured product of the curable composition and the contact layer in the laminate may be reduced.
The component D is not particularly limited as long as it has a lower specific gravity than the whole curable composition and floats on the surface of the curable composition and prevents the components A and B from contacting oxygen, and examples thereof include paraffin. The melting point of the paraffin is preferably 40-80 ℃. When the melting point is 40 ℃ or higher, a sufficient air barrier effect can be obtained when the curable composition is cured, and the surface curability is good. On the other hand, when the melting point is 80 ℃ or lower, the solubility of paraffin in the curable composition becomes good when the curable composition is prepared.
The component D may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
When 2 or more kinds of D components are used in combination, sufficient air-shielding effect can be obtained even when the temperature is changed by using paraffins having different melting points in combination, and surface curability is improved. When used in combination, the melting point difference is preferably about 5 to 20 ℃.
As the component D, a wax dispersed in an organic solvent may be used from the viewpoint of improving surface curability. The wax is preferably dispersed in the organic solvent, and the particle diameter of the dispersed wax is preferably 0.1 to 50 μm. The wax in the dispersed state can effectively exhibit an air shielding effect. The wax in the dispersed state may be added as it is to a commercially available product. Specific examples of the Paraffin wax include Paraffin wax-115 (trade name, melting point: 47 ℃ C. in the catalogue of products manufactured by Japan wax Co., Ltd.), Paraffin wax-130 (trade name, melting point: 55 ℃ C. in the catalogue of products manufactured by Japan wax Co., Ltd.), Paraffin wax-150 (trade name, melting point: 66 ℃ C. in the catalogue of products manufactured by Japan wax Co., Ltd.), and the like.
[ curing method of curable composition ]
The curable composition of the present invention can be cured by a conventional radical polymerization method. For example, redox polymerization methods can be mentioned. In the redox polymerization method, a redox polymerization initiator is added to the curable composition, and a polymerization reaction is carried out by radicals generated by the polymerization initiator, thereby obtaining a cured product of the curable composition.
[ component E and component F ]
The redox polymerization initiator is a polymerization initiator used in combination with a reducing agent of the component E and a curing agent of the component F, and may be contained in the curable composition. Examples of the reducing agent for component E include aromatic tertiary amines, metal soaps, and thiourea compounds. Examples of the curing agent of component F include organic peroxides such as dibenzoyl peroxide (benzoyl peroxide), hydroperoxides, and monocarbonate type peroxides.
Examples of combinations of the component E and the component F that can be used in the redox polymerization initiator include the following (1) to (4).
(1) A combination of an aromatic tertiary amine (component E) and dibenzoyl peroxide (component F).
Specific examples of the aromatic tertiary amines (component E) include, for example, N-dimethyl-p-toluidine, N-diethylaniline, N-diethyl-p-toluidine, N- (2-hydroxyethyl) N-methyl-p-toluidine, N-bis (2-hydroxyethyl) -p-toluidine, N-bis (2-hydroxypropyl) -p-toluidine; ethylene oxide or propylene oxide adducts of N, N-bis (2-hydroxyethyl) -p-toluidine or N, N-bis (2-hydroxypropyl) -p-toluidine, and the like. These aromatic tertiary amines are not limited to p (para) isomers, and may be o (ortho) isomers or m (meta) isomers.
(2) A combination of a metal soap (component E) and a hydroperoxide (component F).
Specific examples of the metal soap (component E) include cobalt naphthenate, copper naphthenate, manganese naphthenate, cobalt octylate, nickel octylate, cobalt acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, iron acetylacetonate, vanadyl acetylacetonate, and vanadium acetylacetonate.
Specific examples of the hydroperoxide (component F) include cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,3, 3-tetramethylbutyl hydroperoxide, tert-butyl hydroperoxide, tert-hexyl hydroperoxide, tert-amyl hydroperoxide, 2, 5-dimethylhexane-2, 5-dihydroperoxide, and the like.
(3) A combination of a thiourea compound (component E) and a hydroperoxide (component F).
Specific examples of the thiourea compound (component E) include thiourea, ethylene thiourea, N '-dimethylthiourea, N' -diethylthiourea, N '-dipropylthiourea, N' -di-N-butylthiourea, N '-dilaurylthiourea, N' -diphenylthiourea, trimethylthiourea, 1-acetyl-2-thiourea, and 1-benzoyl-2-thiourea. Specific examples of the hydroperoxide (component F) include the hydroperoxides exemplified in the above (2).
(4) A combination of a thiourea compound (component E) and a monocarbonate type peroxide (component F).
Specific examples of the monocarbonate type peroxide (component F) include t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy2-ethylhexyl monocarbonate, allylt-butylperoxycarbonate, and 1, 6-bis (t-butylperoxycarbonyloxy) hexane. Specific examples of the thiourea compound (component E) include the thiourea compounds exemplified in the above (3).
These E component and F component can be used alone in 1 kind, or can be used in combination of 2 or more.
From the viewpoint of shortening the gelling time of the curable composition and improving the production efficiency, a combination of the aromatic tertiary amine (component E) and the organic peroxide (component F) is preferable, and a combination of the aromatic tertiary amine (component E) and the dibenzoyl peroxide (component F) is more preferable. From the viewpoint of giving a cured product having high strength and high elongation, the aromatic tertiary amine is preferably at least 1 selected from the group consisting of N, N-dimethyl-p-toluidine, N-diethyl-p-toluidine, N-bis (2-hydroxyethyl) -p-toluidine, and N, N-bis (2-hydroxypropyl) -p-toluidine.
The content of the component E in the curable composition is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and still more preferably 0.3 to 3 parts by mass, based on 100 parts by mass of the total amount of the components A and B. When the content of the component E is more than the above range, the curable composition has better curability, and thus a cured product can have high strength and high elongation. When the content of the component E is less than the above range, the gelation time becomes longer, and the operation such as stirring and injection of the curable composition becomes easier.
On the other hand, the content of the component F in the curable composition is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and still more preferably 0.3 to 3 parts by mass, relative to 100 parts by mass of the total amount of the components a and B. When the content of the component F is within the above range, the curable composition has better curability, and thus a cured product can have high strength and high elongation. When the content of the component F is less than the above range, the gelation time becomes longer, and the operation such as stirring and injection of the curable composition becomes easier.
[ other Components ]
The curable composition of the present invention may contain other components (hereinafter, appropriately referred to as "other components") than the above components a to F within a range not to impair the effects of the present invention.
Examples of the other components include various additives such as rubber, an antioxidant, a plasticizer, an ultraviolet absorber, a thixotropic agent, an antifoaming agent, a polymerization inhibitor, a silane coupling agent, an aggregate, and a pigment; and radical polymerization initiators such as thermal polymerization initiators and photopolymerization initiators.
In the curable composition of the present invention, a rubber may be added to improve the strength and elongation of the cured product. Specific examples of the rubber include, for example, (meth) acrylate-butadiene copolymer, (meth) acrylate-butadiene-styrene copolymer, polybutadiene rubber, chloroprene rubber, acrylonitrile butadiene rubber, and the like.
In the curable composition of the present invention, an antioxidant may be added to prevent oxidative deterioration of a cured product. Specific examples of the antioxidant include phenolic antioxidants such as n-octadecyl 3- (3 ', 5' -di-t-butyl-4 '-hydroxyphenyl) propionate, tetrakis- [ methylene-3- (3', 5 '-di-t-butyl-4' -hydroxyphenyl) propionate ] methane, triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate ], and 1, 6-hexanediol bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ]; phosphorus antioxidants such as triphenyl phosphite, triisodecyl phosphite, tridecyl phosphite, and tris (2, 4-di-t-butylphenyl) phosphite; sulfur antioxidants such as dihexyl sulfide, dilauryl 3,3 '-thiodipropionate, ditridecyl 3, 3' -thiodipropionate, ditetradecyl 3,3 '-thiodipropionate, dioctadecyl 3, 3' -thiodipropionate, and pentaerythritol tetrakis (. beta. -lauryl thiopropionate).
In the curable composition of the present invention, a plasticizer may be added to reduce the hardness of the cured product. Specific examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, di (2-ethylhexyl) phthalate, and diisodecyl phthalate; adipates such as di (2-ethylhexyl) adipate and octyl adipate; sebacates such as dibutyl sebacate and di (2-ethylhexyl) sebacate; dibasic fatty acid esters such as azelaic acid di (2-ethylhexyl) ester and azelaic acid esters such as octyl azelate; paraffins such as chlorinated paraffin, and the like.
In the curable composition of the present invention, an ultraviolet absorber may be added to suppress the photo-aging of the cured product. Specific examples of the ultraviolet absorber include derivatives of 2-hydroxybenzophenone such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-octoxybenzophenone, 2-hydroxy-4-decyloxybenzophenone, 2-hydroxy-4, 4 '-dimethoxybenzophenone and 2-hydroxy-4, 4' -dibutoxybenzophenone; benzotriazole derivatives such as 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole and 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butylphenyl) benzotriazole; halides of these derivatives; phenyl salicylates such as phenyl salicylate and p-tert-butyl salicylate, and derivatives thereof.
In the curable composition of the present invention, a thixotropic agent may be added to suppress sedimentation when the aggregate is added to the curable composition. Specific examples of the thixotropic agent include organic thixotropic agents such as urethane urea, fatty acid amide, organic bentonite, oxidized polyethylene wax and organically modified sepiolite, and inorganic thixotropic agents such as fine silica particles.
In the curable composition of the present invention, an antifoaming agent may be added to remove air bubbles in the curable composition. Specific examples of the defoaming agent include an acrylic defoaming agent in which a specific acrylic polymer is dissolved in a solvent, and a vinyl defoaming agent in which a specific vinyl polymer is dissolved in a solvent. Specific product names of the defoaming agent include, for example, product names manufactured by NATOYZE CHEMICAL CORPORATION: DISPARLON OX-880EF, OX-881, OX-883, OX-77EF, OX-710, OX-8040, 1922, 1927, 1950, P-410EF, P-420, P-425, PD-7, 1970, 230HF, LF-1980, LF-1982, LF-1983, LF-1984, LF-1985, etc., and the product names manufactured by BYK Japan: BYK-052, BYK-1752, etc.
In the curable composition of the present invention, a polymerization inhibitor may be added to improve the storage stability of the curable composition. Specific examples of the polymerization inhibitor include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, and 2, 6-di-tert-butyl-4-methylphenol.
In the curable composition of the present invention, a silane coupling agent may be added to improve the adhesion between the curable composition and the aggregate. Specific examples of the silane coupling agent include 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (glycidyloxypropyl) trimethoxysilane, 3-mercaptopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.
(thermal polymerization initiator)
In the curable composition of the present invention, a thermal polymerization initiator may be added to improve curability of the curable composition. Specific examples of the thermal polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide; peroxyketals such as 1, 1-bis (t-hexylperoxy) -3,3, 5-trimethylcyclohexane, 1-bis (t-hexylperoxy) cyclohexane, and 1, 1-bis (t-butylperoxy) cyclohexane; dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; diacyl peroxides such as dilauroyl peroxide; peroxydicarbonates such as bis (4-t-butylcyclohexyl) peroxydicarbonate and bis (2-ethylhexyl) peroxydicarbonate; peroxides such as peroxy esters such as t-butyl peroxy-2-ethylhexanoate, t-hexylperoxy isopropyl monocarbonate, t-butyl peroxybenzoate, and 1,1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate; azo compounds such as 2,2 ' -azobis (isobutyronitrile), 2 ' -azobis (2-methylbutyronitrile), 2 ' -azobis (2, 4-dimethylvaleronitrile), 1 ' -azobis-1-cyclohexanecarbonitrile, dimethyl-2, 2 ' -azobisisobutyrate, 4 ' -azobis-4-cyanovaleric acid, and 2,2 ' -azobis- (2-amidinopropane) dihydrochloride.
(photopolymerization initiator)
In the curable composition of the present invention, a photopolymerization initiator may be added to improve curability of the curable composition. Specific examples of the photopolymerization initiator include benzophenone, 4-methylbenzophenone, 2,4, 6-trimethylbenzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2-ethylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo { 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone }, benzyldimethyl ketal, 1-hydroxycyclohexylphenylketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-methyl- [4- (methylthio) phenyl ] -2-morpholinyl-1-propanone, and mixtures thereof, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, diethylthioxanthone, isopropylthioxanthone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide, phenylbis (2,4, 6-trimethylbenzoyl) -phosphine oxide, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl ] phenyl } -2-methylpropan-1-one, and methyl benzoylformate.
When the curable composition of the present invention contains a radical polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator, the content of the radical polymerization initiator in the curable composition is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total amount of the components a and B.
When the curable composition of the present invention contains a photopolymerization initiator, the curable composition is irradiated with active energy rays to generate radicals from the photopolymerization initiator and cause radical polymerization, thereby obtaining a cured product of the curable composition. Examples of the active energy ray include an α ray, a β ray, a γ ray, an X ray, an ultraviolet ray, and a visible ray. From the viewpoint of workability and curability, ultraviolet rays are preferred. Examples of the light source for irradiating ultraviolet rays include a high-pressure mercury lamp, a metal halide lamp, a xenon flash lamp, an LED lamp, and a chemical lamp.
(other radical polymerizable monomers)
The curable composition of the present invention may contain other radically polymerizable monomers (hereinafter, appropriately referred to as "monomer G") as polymerizable monomers other than the components a and B. The curable composition of the present invention contains the monomer G, whereby the viscosity and the hardness of a cured product can be more easily adjusted.
Examples of the monomer G include (meth) acrylic monomers other than the components a and B; aromatic vinyl monomers such as styrene and alpha-methylstyrene; vinyl cyanide monomers such as acrylonitrile; vinyl ester monomers such as vinyl acetate. The monomer G may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The content of the monomer G is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less, relative to 100 parts by mass of the total amount of the components a and B. The curable composition containing the monomer G can easily adjust the viscosity and the hardness of a cured product. When the content of the monomer G is more than the above range, the elongation of the cured product tends to be low, and the viscosity tends to be high and the hardness of the cured product tends to be low. When the content of the monomer G is less than the above range, the viscosity of the curable composition and the hardness of the cured product can be adjusted while maintaining the elongation of the cured product.
(aggregate)
The curable composition of the present invention preferably further contains an aggregate for the purpose of suppressing curing shrinkage during molding, improving strength, and further improving durability such as abrasion.
Specific examples of the aggregate include sand, silica sand, river sand, gypsum rubrum, corundum, marble, calcium carbonate, kaolin, bentonite, mica, talc, silicon carbide powder, silicon nitride powder, boron nitride powder, alumina, slag, glass powder, ceramic aggregate, pottery dust, colored aggregate, and the like. These aggregates may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The particle size of the aggregate depends on the thickness of the desired cured product, but the sieved particle size is preferably 5mm or less, more preferably 3mm or less, and still more preferably 2mm or less. The aggregate preferably has a mesh size of 0.01mm or more, more preferably 0.1mm or more. When the particle size of the aggregate is 5mm or less, the cured product can be made thin, and flexibility can be easily obtained. Further, when the particle diameter of the aggregate is 0.01mm or more, the viscosity of the curable composition is low, and fluidity is easily obtained. The particle size distribution of the aggregate is not particularly limited since it is derived from the viscosity of the curable composition, the shape of the aggregate, the thickness of the molded cured product, and the like, and may be appropriately adjusted.
The amount of the aggregate added is preferably 50 to 400 parts by mass, more preferably 75 to 350 parts by mass, and still more preferably 100 to 300 parts by mass, per 100 parts by mass of the curable composition. When the amount of the aggregate added is 50 parts by mass or more, the strength and abrasion resistance of the cured product of the curable composition can be improved. When the amount of the aggregate added is 400 parts by mass or less, not only the strength and abrasion resistance of the cured product of the curable composition can be improved, but also cracks are less likely to occur.
(pigment)
The curable composition of the present invention may contain a pigment for coloring. Examples of the pigment include organic pigments such as azo pigments and phthalocyanine pigments; ceramic pigments, inorganic pigments such as iron oxide and titanium oxide, and the like. These pigments may be used alone in 1 kind, or may be used in combination in 2 or more kinds. The amount of the pigment added is preferably 1 to 15 parts by mass, more preferably 2 to 10 parts by mass, per 100 parts by mass of the curable composition. When the amount of the pigment is 1 part by mass or more, the coloring is good, and when the amount is 15 parts by mass or less, the elongation of the cured product is good.
< method for producing curable composition >
The above-described method for producing the curable composition includes a method of mixing the components a to D with a conventional mixer to prepare a slurry mixture. When the curable resin composition is cured, a method of adding a curing agent to the curable composition (for example, the slurry mixture) immediately before the curing reaction proceeds is preferable. When the curing is performed by redox polymerization, a method of adding the component F (curing agent) to the curable resin composition (for example, the slurry mixture) immediately before the curing reaction proceeds is preferable. The component E (reducing agent) may be premixed with the components A to D. In the case of preparing a curable resin composition (for example, the slurry mixture) before adding the curing agent, other components may be added as necessary.
Examples of the method for mixing the components A to D and, if necessary, the components E, F and other components include a method of stirring and mixing at room temperature and a method of heating and mixing them. When the mixing is carried out by heating and mixing, the compatibility becomes good, and from the viewpoint of enabling more uniform mixing, the mixing is preferably carried out under heating at 40 to 100 ℃, and the stirring time for the mixing is preferably in the range of 0.1 to 5 hours.
< viscosity of curable composition >
The viscosity of the curable composition (slurry mixture) other than the component F to which the curing agent is added is preferably 2 to 1000 mPas, more preferably 3 to 500 mPas, and still more preferably 5 to 300 mPas as measured at 23 ℃ with a B-type viscometer. When the viscosity of the curable composition is within the above range, sedimentation of aggregate in the curable composition can be prevented, and the curable composition can easily flow into a mold.
< gelation time of curable composition >
The gelation time of the curable composition is preferably 3 to 45 minutes, more preferably 5 to 40 minutes, and further preferably 8 to 35 minutes, from the time when the component F is added to the curable composition (slurry mixture) mixed with components other than the component F at 23 ℃. When the gelation time of the curable composition is within the above range, productivity and workability are improved.
[ molded article (cured article) ]
The molded article of the present invention is a cured product of the curable composition of the present invention.
As a method for producing a molded article, a method is preferred in which a liquid curable composition (slurry mixture) in which components a to D, and if necessary, component E and other components are mixed in advance is prepared, component F (curing agent) is further added, the mixture is charged into a mold, a polymerization reaction is started, curing is performed, and the molded article is obtained by demolding. The curing temperature after adding the component F (curing agent) is preferably 5 to 65 ℃, more preferably 10 to 60 ℃, and further preferably 15 to 55 ℃. When the temperature is 5 to 65 ℃, the curing reaction of the curable resin composition is sufficiently advanced, and the properties of the cured product are improved. The curing time varies depending on the curing temperature, and is preferably 10 minutes to 24 hours.
In order to suppress air bubbles in the cured product, the curable composition may be subjected to a defoaming treatment such as vacuum defoaming or vibration defoaming. When the component F is added, the component F may be added and then subjected to defoaming treatment.
A method of pouring the curable composition into a mold having irregularities or a specific shape and curing the composition or the like can obtain a cured product (molded product) having irregularities or a specific shape. The method is suitable for obtaining a cured sheet such as a sheet for a blind sidewalk brick.
[ laminate (Blind road brick) ]
The laminate of the present invention contains a molded article and a substrate of a cured product of the curable composition.
Examples of the shape of the molded article include a sheet shape, a block shape, a tile shape, a linear shape, a dot shape, and the like.
The shape of the molded article is preferably a sheet shape from the viewpoint of workability when the molded article is attached to a base material.
For example, when the sheet is used as a guide sign for visually impaired people such as a blind sidewalk block or a blind sidewalk tile having irregularities such as lines and dots, the sheet is preferably a sheet-like formed product (sheet for a blind sidewalk tile) having a linear shape and a dotted shape.
Examples of the type of the base material include concrete, asphalt, mortar, wood, polypropylene resin, epoxy resin, acrylic resin, and urethane resin.
From the viewpoint of adhesiveness, concrete, asphalt, and mortar are preferable as the base material.
The molded product preferably further contains an aggregate for the purpose of suppressing curing shrinkage during molding, improving strength, and further improving durability such as abrasion.
A laminate comprising such a sheet-like shaped article (sheet for a blind sidewalk brick) and a substrate is suitable for use as a blind sidewalk brick.
The method for producing the laminate (for example, a sidewalk brick) is not particularly limited, and examples thereof include a method in which a curable resin composition (or a mixture of the curable resin composition and an aggregate added as needed or a pigment further contained) is poured into a resin mold made of polypropylene or silicone resin, cured at 5 to 65 ℃ for 10 minutes to 24 hours, and then released from the mold, and the obtained molded article is laminated on a substrate.
As a method for laying the obtained molded article (for example, a sheet for a blind sidewalk brick), a method of adhering to a substrate with an adhesive is exemplified. For example, a laminate (blind bricks) in which a concrete base material/adhesive/blind brick sheet is laminated in this order can be produced and laid by sticking the blind brick sheet to the concrete base material with an adhesive.
Examples
The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples and comparative examples, "part" means "part by mass".
< determination of weight average molecular weight >
The weight average molecular weights (Mw) of the acrylic polymer a and the acrylic polymer B were calculated in terms of standard polystyrene under the following measurement conditions.
GPC apparatus: HLC-8120 available from Tosoh corporation
A chromatographic column: chromatography column manufactured by Tosoh corporation (TSKgel SuperHM-HX 4, TSKguardcolumn SuperH-H)
Sample solution: 20. mu.L of a 0.3% by mass THF solution of an acrylic polymer
Flow rate: 0.6 mL/min
Eluent: THF (stabilizer: BHT (butylated hydroxytoluene))
Temperature of the column: 40 deg.C
Production example 1 production of acrylic Polymer A
145 parts of deionized water and 0.5 part of polyvinyl alcohol (saponification rate: 80%, polymerization degree: 1700) as a dispersion stabilizer were put into a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, and stirred. After the polyvinyl alcohol was completely dissolved, the stirring was stopped, and 60 parts of Methyl Methacrylate (MMA), 40 parts of n-butyl methacrylate (n-BMA), 0.1 part of 2, 2' -Azobisisobutyronitrile (AIBN) and 0.5 part of n-octylmercaptan were added and the mixture was stirred again. The atmosphere in the polymerization apparatus was replaced with nitrogen under stirring, and the temperature was raised to 70 ℃ to carry out polymerization. After the exothermic peak of polymerization was detected, the temperature was raised to 98 ℃ and the reaction was continued for 0.5 hour, followed by cooling to 40 ℃. The resulting aqueous suspension was filtered through a nylon filter cloth having a pore size of 45 μm, and the filtrate was washed with deionized water. After dehydration, the resulting mixture was dried at 40 ℃ for 20 hours to obtain a granular (meth) acrylic polymer (hereinafter referred to as "acrylic polymer A"). The weight average molecular weight (Mw) of the acrylic polymer A was 42000.
Production example 2 production of acrylic Polymer B
An acrylic polymer B was produced and the weight average molecular weight was measured in the same manner as in production example 1, except that the kind and amount of the raw materials were changed to the conditions shown in table 1. The details of the symbols and abbreviations in table 1 are shown in manufacturing example 1 and table 3.
[ TABLE 1]
Figure BDA0002723867580000201
(example 1)
1. Production of curable composition
A reaction vessel equipped with a cooler was charged with 40 parts by mass of methyl methacrylate, 20 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of N-butyl acrylate, 5 parts by mass of ethoxylated bisphenol A diacrylate (trade name: "New Frontier BPE-4", manufactured by first Industrial pharmaceutical Co., Ltd.), 0.2 part by mass of paraffin 130 (trade name "paraffin wax-130", manufactured by Japan Seikagaku corporation), and 1 part by mass of N, N-bis (2-hydroxyethyl) -p-toluidine (trade name: PTEO ", manufactured by Japan emulsifier Co., Ltd.) as the component D.
While these components in the reaction vessel were stirred, 15 parts of acrylic polymer a produced in production example 1 was added as component B. Subsequently, the solution in the reaction vessel was heated to 60 ℃ and stirred for 2 hours while maintaining the temperature. After confirming that the acrylic polymer A was completely dissolved, the solution in the reaction vessel was cooled to 23 ℃ and 0.25 part by mass of pentaerythritol tetrakis (3-mercaptobutyrate) (PETMB) as a component C was added thereto, and the mixture was stirred for 30 minutes while maintaining the temperature, thereby obtaining a slurry mixture.
To the resulting slurry mixture, 2 parts of Perkadox CH-50L (mixture of benzoyl peroxide and dicyclohexyl phthalate, product name: "Perkadox CH-50L" manufactured by Akzo Co., Ltd., chemical product, content of benzoyl peroxide: 50% by mass) as component F was added, followed by stirring to obtain a curable composition.
2. Production of sheet-like molded article
The obtained curable composition was poured into a mold having a length of 100mm, a width of 100mm and a height of 2mm, which was made of a PET film to which a polyurethane sponge tape having a height of 2mm was attached. After curing at 23 ℃ for 24 hours, the cured product was peeled off to obtain a sheet-like molded article having a length of 100mm, a width of 100mm and a height of 2 mm.
3. Evaluation of sheet-shaped molded article
[ curability ]
The tack-free time (time taken until tack-free after addition of Perkadox CH-50L) of the curable composition in the mold in the production of the above sheet-like cured product was measured, and the curability was evaluated according to the following evaluation criteria.
Evaluation criteria
Very good: the surface drying time is less than 120 minutes
Good: the surface drying time is more than 120 minutes and less than 180 minutes
X: the surface drying time is more than 180 minutes
[ adhesiveness ]
Acryspirup DR-460 (product name "Acryspirup DR-460" manufactured by Ciba corporation) 600g and Nyper NS (suspension of dibenzoyl peroxide (purity: 40%), product name: "Nyper NS") 18g were put into a 500mL polypropylene container, stirred with a Teflon (registered trademark) stirring rod, and mixed uniformly to prepare an adhesive.
The adhesive thus obtained was uniformly applied to a slate plate (according to JIS K5430) by a trowel, and had a length of 150mm, a width of 150mm and a height of 10 mm. The sheet-shaped molded article obtained as described above was then stuck. In addition, when a sheet-like molded article was produced, the surface (surface in contact with air during curing) was adhered in contact with an adhesive and cured for 24 hours.
On the sheet-like molded article thus bonded, a notch having a width of 30mm and a length of 60mm was formed by cutting into the sheet-like molded article from the end thereof to the base slate plate using a diamond cutter, and the sheet-like molded article was peeled off by applying an impact from the edge cutting direction to the adhesive surface with a hammer.
The cohesive failure rate (the ratio of the area of cohesive failure of a slab or a cured adhesive) at the peeled portion was observed and evaluated according to the following evaluation criteria.
Evaluation criteria
Very good: the cohesive failure rate is more than 90 percent
Good: the cohesive failure rate is more than 50 percent and less than 90 percent
X: cohesive failure rate is less than 50%
The curability of the curable composition and the evaluation results of the adhesiveness of the sheet-like molded article are shown in table 2. The numerical values of the respective components in table 2 represent parts by mass. The details of the symbols and abbreviations in table 2 are shown in table 3.
(examples 2 to 9, comparative examples 1 to 3)
Curable compositions and sheet-like molded articles were produced in the same manner as in example 1 except that the formulation composition shown in table 2 was changed, and various evaluations were performed. The evaluation results are shown in table 2.
[ TABLE 2]
Figure BDA0002723867580000221
[ TABLE 3]
Figure BDA0002723867580000222
Figure BDA0002723867580000231
As shown in Table 2, the curable compositions of examples 1 to 9 were excellent in curability and the sheet-like molded articles thereof were excellent in adhesion.
On the other hand, the curable composition of comparative example 1 contained a large amount of component D, and therefore the adhesiveness of the sheet-like molded product was poor. The curable composition of comparative example 2 has poor curability because it does not contain component D. The curable composition of comparative example 3 has poor curability because it contains no component C.
(example 10)
1. Manufacture of sheet material for blind sidewalk brick
100 parts of silica sand No. 7 (trade name: Sanhe silica sand No. 7) as an aggregate, 6 parts of a WHITE inorganic pigment (trade name: CR-50 (titanium oxide WHITE product) manufactured by Shinetien corporation) and 4 parts of a yellow inorganic pigment (trade name: Bayferrox 920G manufactured by LANXESS corporation) were added to 100 parts of the curable composition manufactured in example 1 at 23 ℃ and the mixture was stirred and mixed for 2 minutes (rotation speed: 1000rpm) by a homogenizer to obtain a curable aggregate. The obtained curable aggregate additive was poured into a warning mold having a length of 30cm, a width of 30cm and a thickness of 2mm, and defoaming treatment was carried out by a shaker, followed by curing at 23 ℃ for 24 hours and then demolding to obtain a sheet for blind bricks (having a length of 30cm, a width of 30cm and a thickness of 2 mm).
2. Evaluation of sheet for Blind road brick
[ curability ]
The open time of the curable aggregate additive in the mold (the time from the addition of Perkadox CH-50L to the non-tackiness of the curable aggregate additive in the mold in the production of the curable composition) was measured during the production of the sheet for a sidewalk brick described above, and the curability was evaluated according to the following evaluation criteria.
Evaluation criteria
Very good: the surface drying time is less than 180 minutes
Good: the surface drying time is more than 180 minutes and less than 240 minutes
X: the surface drying time is more than 240 minutes
[ adhesiveness ]
Acryspirup DR-460 (product name "Acryspirup DR-460" manufactured by Ciba corporation) 600g and Nyper NS (suspension of dibenzoyl peroxide (purity: 40%), product name: "Nyper NS") 18g were put into a 500mL polypropylene container, stirred with a Teflon (registered trademark) stirring rod, and mixed uniformly to prepare an adhesive.
The adhesive thus obtained was uniformly applied to a slate plate (according to JIS K5430) by a trowel, and had a size of 350mm in length, 350mm in width and 10mm in height. The patch for street tape obtained as described above was then stuck. In addition, in the production of the sheet for a blind sidewalk brick, the surface (surface in contact with air during curing) was bonded in contact with an adhesive and cured for 24 hours.
On the adhered sheet for blind sidewalk bricks, a diamond cutter was used to cut into the sheet for blind sidewalk bricks from the end thereof to the base slate plate to form a notch having a width of 30mm and a length of 60mm, and the sheet was peeled off by applying an impact from the cutting direction of the end to the adhesion surface with a hammer.
The cohesive failure rate (the ratio of the area of cohesive failure of a slab or a cured adhesive) at the peeled portion was observed and evaluated according to the following evaluation criteria.
Evaluation criteria
Very good: the cohesive failure rate is more than 90 percent
Good: the cohesive failure rate is more than 50 percent and less than 90 percent
X: cohesive failure rate is less than 50%
The results of the evaluation of the curability of the curable aggregate additive and the adhesion of the sheet for a sidewalk brick are shown in table 4. The values of the curable composition and each component in table 4 show parts by mass. The details of the symbols and abbreviations in table 4 are shown in tables 2 and 5.
(examples 11 to 15, comparative examples 4 and 5)
Curable aggregate additives and sheets for sidewalk blocks were produced in the same manner as in example 10 except that the formulation composition shown in table 4 was changed, and various evaluations were performed. The evaluation results are shown in table 4.
[ TABLE 4]
Figure BDA0002723867580000251
[ TABLE 5]
No. 7 silica sand Trade name manufactured by Sanhe corporation: sanhe silica sand No. 7
CR-50 Trade name manufactured by stone industries: CR-50 (titanium oxide WHITE product)
Bayferrox 920G Manufactured by LANXESS corporation, trade name: bayferrox 920G
As shown in Table 4, the curable aggregate additives of examples 10 to 15 using the curable compositions prepared in examples exhibited good curability, and the sheets for sidewalk tiles exhibited good adhesiveness.
On the other hand, the curable aggregate additive of comparative example 4 using the curable composition prepared in comparative example 1 contained a large amount of the component D, and therefore, the adhesion of the sheet for a blind sidewalk brick was poor. Comparative example 5 using the curable composition prepared in comparative example 3 had poor curability because it contained no component C.
Industrial applicability
The present invention provides a curable composition having good curability and a molded article having good adhesion to a substrate. Therefore, a laminate in which a molded article is bonded to a base material via an adhesive, such as a blind sidewalk brick, is suitably obtained.

Claims (11)

1. A curable composition comprising: a monomer A having at least 1 (meth) acryloyl group in the molecule,
At least 1 compound B selected from acrylic polymers, urethane (meth) acrylates, epoxy (meth) acrylates and polyester (meth) acrylates, polyfunctional mercapto compounds C and waxes D,
the content of the wax D is 0.01-0.4 parts by mass relative to 100 parts by mass of the total amount of the monomer A and the compound B.
2. The curable composition according to claim 1, wherein the polyfunctional mercapto compound C is a polyfunctional mercapto compound having a secondary or higher mercapto group.
3. The curable composition according to claim 1, wherein the polyfunctional mercapto compound C is a polyfunctional mercapto compound having 4 or more secondary or more mercapto groups.
4. The curable composition according to any one of claims 1 to 3, further comprising a reducing agent E and a curing agent F.
5. The curable composition according to any one of claims 1 to 4, wherein the content of the compound C is 0.05 to 2 parts by mass relative to 100 parts by mass of the total amount of the monomer A and the compound B.
6. The curable composition according to any one of claims 1 to 5, wherein the curable composition is a curable composition for sidewalk tiles.
7. A molded article comprising a cured product of the curable composition according to any one of claims 1 to 6.
8. The shaped article according to claim 7, wherein the solidified article contains an aggregate.
9. The molding according to claim 7, wherein the molding is a sheet for a blind sidewalk brick.
10. A laminate comprising the shaped article according to any one of claims 7 to 9 and a substrate.
11. The laminate of claim 10, wherein the laminate is a sidewalk tile.
CN202011096298.2A 2019-11-07 2020-10-14 Curable composition, molded article, and laminate Pending CN112778462A (en)

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CN107001631A (en) * 2014-12-22 2017-08-01 昭和电工株式会社 Actinic-radiation curable composition and application thereof
CN108699356A (en) * 2016-03-15 2018-10-23 阿科玛法国公司 The coating and encapsulant composition of free-radical curable with improved surface cure property
JP2019019307A (en) * 2017-07-19 2019-02-07 株式会社菱晃 Acrylic resin composition and laminate

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102906137A (en) * 2010-06-18 2013-01-30 Dic株式会社 Urethane (meth)acrylate resin composition and coating material using same
CN103492423A (en) * 2011-10-14 2014-01-01 三菱丽阳株式会社 Resin composition, primer for metal base, and laminated body and method for manufacturing same
CN107001631A (en) * 2014-12-22 2017-08-01 昭和电工株式会社 Actinic-radiation curable composition and application thereof
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