JP2001011396A - Application of sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an application method of a sheet without requiring the coating of a paste or water at the time of sticking, capable of facilitating the positioning at the time of sticking, and good in operability. SOLUTION: A sheet produced by the following method and having a resin layer is preheated and temporarily stuck to the surface of a material to be stuck, and the temporarily stuck sheet is mainly heated to mainly stick the sheet on the material to be stuck in the method for applying the sheet: the forming method of the resin layer comprises coating an aqueous emulsion-type heat-sensitive tacky adhesive composition comprising (A) a water-soluble resin having a hydrophilic part with >=20 deg.C glass transition temperature, and (B) a polymer obtained by carrying out an emulsion polymerization of a radically polymerizable monomer, and having <=-20 deg.C glass transition temperature, and drying the coated product at a temperature of an adhesion-exhibiting temperature or less of the pressure-sensitive adhesive. The resin layer is removable and non-adhesive before the preheating, slightly adhesive after the preheating and highly adhesive after the main heating.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of applying a sheet, and more particularly, to a method of applying a sheet which does not require application of glue or water at the time of application and which can be easily positioned at the time of application and has good workability. . INDUSTRIAL APPLICABILITY The method of the present invention is suitable as a method for applying an indoor decorative sheet represented by fusuma paper, wallpaper, and the like.

[0002]

2. Description of the Related Art Conventionally, indoor decorative sheets such as fusuma paper and wallpaper are coated with a water-soluble glue on a sheet base material during construction.
While this paste was not completely dried and was sticky, it was constructed by attaching a sheet to an adherend such as a sliding door or a wall. However, this method requires a large amount of work space to apply the glue, the work time from applying the glue to pasting is limited, and the work requires skill, such as at home. It was inconvenient to construct in

In order to remedy this inconvenience, a water-soluble paste such as polyvinyl acetate is applied to a sheet substrate in advance, and dried to make it non-adhesive, and the glue surface of the sheet is wetted during construction. A re-wet sheet that is used by expressing the adhesiveness of the paste is also commercially available. However, according to the rewet sheet, the above-mentioned problem of the work space is solved, but instead, the work of moistening the sheet is required, and the above-mentioned problem of the work time is not solved. If a hot-melt adhesive is used instead of a water-soluble glue, it is not necessary to use water at the time of application, but since such an adhesive cures immediately due to a decrease in temperature, it once adheres to the surface of the adherend. There is a problem that it is difficult to reattach after disposing.

As another method, a tack-type sheet in which a pressure-sensitive adhesive is applied to a sheet base material in advance and a release paper is placed thereon is also commercially available. According to this sheet, the adhesiveness appears only by removing the release paper without the need for rewetting, and the adhesiveness is not lost over time, so that the above-mentioned problems can be solved. However, on the other hand, there is a problem of cost increase and dust generation due to the use of release paper, and it is difficult to re-attach like a hot melt adhesive. Further, there has been proposed a sheet in which a so-called delate tack-type adhesive in which a crystalline plasticizer such as dicyclohexyl phthalate is mixed with a thermoplastic resin such as an ethylene-vinyl acetate copolymer is applied. Such a sheet does not require a release paper because it is normally non-adhesive, and develops adhesiveness by heat treatment during construction. However, the cohesive force of the adhesive is extremely reduced because the thermoplastic resin is softened by the crystalline plasticizer melted by this heat treatment, and when the sheet is peeled off after being temporarily bonded for positioning, adhesive residue remains on the adherend. Therefore, it is difficult to re-attach the sheet. In addition, other problems arise, such as the crystalline plasticizer which has been liquefied by the heat treatment being transferred to the surface through the sheet substrate and impairing the appearance of the sheet.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method of applying a sheet which does not require application of glue or water at the time of sticking, is easy to position at the time of sticking, and has good workability. .

[0006]

Means for Solving the Problems The present inventors constructed a sheet having a non-adhesive resin layer formed by a predetermined component and a method by changing the adhesive force stepwise by heating during use. The inventors have found that the above-mentioned problems can be solved, and completed the present invention.

[0007] In the method for applying a sheet according to the first invention in the present invention, a sheet having a resin layer formed by the following method is preheated and temporarily adhered to the adherend surface, and then the sheet is fully heated. A method for applying a sheet, wherein the sheet is permanently adhered to the adherend, wherein the resin layer is non-adhesive before the preheating and has a low tackiness that has removability after the preheating. Yes, it is characterized by high tackiness after the main heating. [Method of Forming Resin Layer] (A) A hydrophilic portion is provided on the surface of the sheet substrate, and the glass transition temperature of the hydrophilic portion is 20 ° C.
An aqueous emulsion type heat-sensitive adhesive composition comprising the above water-soluble resin and (B) a polymer having a glass transition temperature of −20 ° C. or lower obtained by emulsion polymerization of a radical polymerizable monomer is applied. Then, the heat-sensitive adhesive is dried at a temperature not higher than the temperature at which the heat-sensitive adhesive is developed.

[0008] The sheet before the preheating is ASTM.
Temperature 2 by T peeling method specified in D1876-61T
The peel strength at 5 ° C. is 10 g / 25 mm or less,
The sheet after the preheating is JIS Z 0237
The peel strength at a temperature of 25 ° C. according to the 180 ° peeling method specified in the above is in the range of 20 to 300 g / 25 mm, and the sheet after the main heating is JIS Z 023.
The peel strength at a temperature of 25 ° C. according to the 180 ° peeling method specified in No. 7 is preferably 500 g / 25 mm or more.

The present invention is suitable as a method for constructing indoor decorative sheets such as fusuma paper, wallpaper, shoji paper, ceiling paper, etc.
It is particularly suitable as a method for applying fusuma paper or wallpaper.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the following, acryl and / or methacryl are referred to as “(meth) acryl”, and acrylate and / or methacrylate are referred to as “(meth) acrylate”. In this specification, the “glass transition temperature” (hereinafter, also referred to as “Tg”) of a polymer refers to a value obtained from the following calculation formula. It should be noted that only Tg used in this formula is expressed in absolute temperature (K), and Tg used in other parts of the specification is expressed in degrees Celsius (° C.).

[0011]

1 / Tg = {W (a) / Tg (a)} + {W (b) / Tg (b)} + ... In the above formula; Tg = Tg of the polymer (K) W (a) = weight fraction of structural unit consisting of monomer (a) in polymer W (b) = weight fraction of structural unit consisting of monomer (b) in polymer Tg (a) ) = Glass transition temperature (K) of homopolymer of monomer (a) Tg (b) = Glass transition temperature (K) of homopolymer of monomer (b)

[I] Heat-Sensitive Adhesive Composition First, the heat-sensitive adhesive composition used in the construction method of the present invention will be described. (1) About Component A (1-1) Acid Value Component A, which is one component of the heat-sensitive adhesive composition used in the application method of the present invention, is a water-soluble resin having a hydrophilic portion having a Tg of 20 ° C. or more. Although not particularly limited, the acid value is 1 meq /
g or more (more preferably 1 to 5 meq / g) of the resin is preferably a water-soluble resin neutralized with a base.
When the acid value is less than 1 meq / g, the solubility of the component A in water tends to be insufficient, so that the liquid stability of the heat-sensitive adhesive composition is reduced or the emulsion polymerization of the component B in the presence of the component A When carrying out, the polymerization stability may be reduced. In this specification, the “acid value” refers to an acid value per solid content of a resin or a polymer, and refers to a theoretical acid value calculated by an ordinary method. When the polymer or resin is neutralized with a base, it indicates the acid value before neutralization. “Meq / g” used as a unit of the acid value represents the number of milligram equivalents of acid in 1 g of the solid content of the resin or polymer.

(1-2) Composition A preferable example of the component A is a copolymer comprising a radical polymerizable monomer unit having an acidic group such as a carboxyl group or a sulfonic acid group and another radical polymerizable monomer unit. And at least Tg of the hydrophilic portion thereof is 20
And the like having an acid value of not less than ° C and the above range. Among them, copolymers having α, β-ethylenically unsaturated carboxylic acid units and hydrophobic radically polymerizable monomer units as main constituent units are more preferably used.

The α, β-ethylenically unsaturated carboxylic acid which gives the α, β-ethylenically unsaturated carboxylic acid unit includes, for example, acrylic acid, methacrylic acid, crotonic acid,
Maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride and the like can be mentioned.
Species or two or more can be used. The amount of the α, β-ethylenically unsaturated carboxylic acid that gives the above-mentioned preferred acid value varies depending on the kind of the unsaturated carboxylic acid used, but is based on the total weight of all the monomers used for the synthesis of the component A. Usually, it is preferably about 3 to 40% by weight.

The radical polymerizable monomer used together with the α, β-ethylenically unsaturated carboxylic acid is water 100
Hydrophobic radically polymerizable monomers having a solubility in g of 2 g or less are preferable, for example, methyl methacrylate,
Ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate,
Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Alkyl (meth) acrylates such as n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate and isononyl (meth) acrylate; styrene, α-methylstyrene, vinyltoluene, etc. And the like. The amount of these monomers to be used is preferably 30 to 80% by weight based on the total amount of all the monomers used for the synthesis of the component A.

In order to synthesize the component A, the above α,
A hydrophilic radically polymerizable monomer other than β-ethylenically unsaturated carboxylic acid may be used if necessary. Examples of such a hydrophilic radical polymerizable monomer include methyl acrylate, vinyl acetate, acrylonitrile, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and polyethylene glycol mono (meth) acrylate. A) acrylate, polypropylene glycol mono (meth) acrylate, (meth) acrylamide, N-methylolacrylamide, glycidyl methacrylate, styrenesulfonic acid and its sodium salt, and 2-acrylamide-2-methylpropanesulfonic acid and its sodium salt Is mentioned.

The component A may be a base neutralized product of the graft copolymer. As this graft copolymer,
A graft copolymer comprising a hydrophilic main chain and a hydrophobic side chain, or a graft copolymer comprising a hydrophobic main chain and a hydrophilic side chain is preferably used. In this case, since the affinity between the hydrophobic part of the component A and the component B is high, the heat-sensitive adhesive composition is excellent in liquid stability.

Component A is obtained by neutralizing a part or all of acidic groups, for example, carboxyl groups, of the copolymer synthesized as described above with a base. As the base used for neutralization, ammonia, amines, alkali metal hydroxides, alkaline earth metal salts and the like can be used. Among these, it is preferable to use a base having a boiling point of 110 ° C. or lower, such as ammonia, methylamine, ethylamine, propylamine, and isopropylamine, and it is particularly preferable to use ammonia. The component A in the present invention may not necessarily be completely neutralized, but must be neutralized to the extent that the component A becomes water-soluble. Specifically, it is preferable that 30 mol% or more of the acidic group of the component A is neutralized, and it is more preferable that 50 mol% or more is neutralized.

The component A is preferably a resin having a low crosslinking density or a substantially non-crosslinked resin. Component A
Is excessively crosslinked, the solubility of this component A in water tends to be insufficient. If the crosslinking density of the component A is too high, it may be difficult to change the adhesiveness of the resin layer when heated (preheating and / or main heating) during application.

(1-3) Glass transition temperature (Tg) Component A is a water-soluble resin having a hydrophilic portion, and the Tg of the hydrophilic portion is 20 ° C. or more (more preferably 30 ° C.).
To 130 ° C, more preferably 40 to 120 ° C). Here, the phrase “the component A has a hydrophilic portion” means that the entire component A may be a hydrophilic portion, or that the component A may be composed of a hydrophilic portion and a hydrophobic portion.
Examples of the component A composed of a hydrophilic portion and a hydrophobic portion include the above-described graft copolymer and block copolymer. When the component A is a graft copolymer as described above, the Tg of the hydrophilic portion is 20 ° C. or higher (more preferably 30 to 130 ° C., further preferably 4 ° C.).
(0 to 120 ° C.), the Tg of the entire component A is not particularly limited.
° C (more preferably -20 to 60 ° C, still more preferably 0 ° C or more and less than 20 ° C). In addition, the Tg of the hydrophobic portion of the graft copolymer is preferably -20 ° C or lower (more preferably -30 ° C or lower, further preferably -40 ° C or lower).

When the Tg of the hydrophilic portion of the component A is less than the above range, it is difficult to make the resin layer non-adhesive before application (before preheating), and the blocking resistance during storage of the sheet is reduced. Easier to do. On the other hand, when the Tg of the hydrophilic portion of the component A, or the Tg of the entire component A or the Tg of the hydrophobic portion exceeds each of the preferred upper limits described above,
The heating temperature required to change the adhesiveness of the resin layer during construction increases, which is not preferable because the energy cost increases.

(1-4) Molecular Weight and Molecular Weight Distribution The number average molecular weight of the component A is preferably from 1,000 to 50,000. If the number average molecular weight is less than 1,000, the water resistance of the resin layer tends to be insufficient. On the other hand, when the number average molecular weight exceeds 50,000, the viscosity becomes high and the production of component A becomes difficult, and the solubility of component A in water becomes insufficient and the liquid stability of the heat-sensitive adhesive composition becomes poor. Is reduced, or when the emulsion polymerization of the component B is performed in the presence of the component A, the polymerization becomes unstable. In addition, when heated during construction, it may be difficult to change the adhesiveness of the resin layer. In order to adjust the number average molecular weight, a chain transfer agent may be appropriately added to the polymerization system.

The ratio of the weight average molecular weight Mw of the component A to the number average molecular weight Mn (hereinafter referred to as “Mw / Mn ratio”) is as follows.
It is preferably at most 3.0, more preferably at most 2.0, even more preferably at most 1.5. The lower limit of the Mw / Mn ratio is usually 1.05 or more, preferably 1.2 or more. Mw / M of component A
As the n-ratio is smaller, the non-adhesive resin layer formed by using the heat-sensitive adhesive composition comprising the component A is more excellent in blocking resistance.

(1-5) Production method of component A When component A is a polymer of a radical polymerizable monomer, a known method can be used as a polymerization method for obtaining component A. . Among them, it is preferable to use a solution polymerization method or an emulsion polymerization method using a radical polymerization initiator from the viewpoint of easiness of polymerization operation, easiness of molecular weight control, and the like.

In the above solution polymerization method, component A can be obtained smoothly by dissolving the above radical polymerizable monomer in an organic solvent and conducting polymerization using an appropriate radical polymerizable initiator. As the organic solvent, one or more organic solvents selected from ketones, acetates, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols and the like can be used. It is preferable to use methyl ethyl ketone from the viewpoint of raw material cost and ease of solvent removal. As the radical polymerization initiator used in the solution polymerization, any of those used in general radical polymerization can be used. The preferred amount of the polymerization initiator to be used is 0.1 to 5% by weight based on the total amount of the monomers.

When the above component A is produced by an emulsion polymerization method, the radical polymerizable monomer is mixed and dispersed in water together with an emulsifier as disclosed in, for example, JP-A-6-271779. The above component A can be smoothly obtained by preparing a monomer emulsion by means of a continuous polymerization method using a suitable radically polymerizable initiator and continuously adding it to a reactor.

In particular, in order to obtain a homogeneous and stable component A, the amount of each monomer charged at each stage of the polymerization is adjusted so that the ratio of the monomers present in the reaction system is kept constant. Controlled polymerization can be performed. In particular,
Among the monomers used for the synthesis of component A, monomers having poor copolymerizability and having a low reaction rate in copolymerization are charged into the reactor at the beginning of the polymerization, and a part or all of the monomers are charged into the reactor to start the polymerization reaction. The monomer having a high reaction rate is dropped into the reactor while the copolymerization proceeds, or substantially all of the monomer having a low reaction rate and a part of the monomer having a high reaction rate are added. Into the reactor to start the polymerization reaction, and according to the consumption rate of the monomer having the fast reaction rate, the monomer having the fast reaction rate is dropped into the reactor, and the composition and the molecular weight are reduced. A substantially uniform component A can be produced. Here, the fast or slow reaction rate refers to a relative rate when each monomer used for the synthesis of the component A is compared.

(2) Component B Component B, which is one component of the heat-sensitive adhesive composition used in the application method of the present invention, has a Tg of −20 ° C. obtained by emulsion polymerization of a radical polymerizable monomer. These are the following polymers. (2-1) Glass transition temperature (Tg) The Tg of the component B must be −20 ° C. or less,
The temperature is preferably -50 ° C or lower. Component B has a Tg of-
If the temperature is higher than 20 ° C., the adhesive strength after the preheating is insufficient, so that temporary fixing becomes difficult, and the adhesive strength after the main heating is insufficient, and the sheet may be peeled off from the adherend after construction.

(2-2) Composition As the component B, various polymers obtained by emulsion polymerization of a radical polymerizable monomer and having a Tg satisfying the above range can be used. For example, an emulsion polymer of a radical polymerizable monomer having (meth) acrylic acid ester as a main component (hereinafter referred to as “acrylic monomer”), a radical polymerizable monomer having ethylene and vinyl ester as a main component. Polymer (hereinafter, referred to as “ethylene-vinyl ester monomer”), a conjugated diene monomer, and a monomer copolymerizable with the conjugated diene monomer (hereinafter, referred to as “conjugated diene monomer”). An emulsion polymer of a radical polymerizable monomer having a main component of “monomer”) can be used.

The vinyl ester monomers in the ethylene-vinyl ester monomers include vinyl acetate,
Vinyl propionate, vinyl butyrate, vinyl pivalate,
Examples include vinyl laurate and vinyl versatate. Examples of the conjugated vinyl monomer in the conjugated vinyl monomer include butadiene, isoprene, chloroprene, and isobutylene.

And, as the acrylic monomer,
Another radically polymerizable monomer (hereinafter, sometimes referred to as a “copolymerizable monomer”) containing (meth) acrylic acid alkyl ester as a main component and copolymerizable therewith as necessary. A small amount, preferably 40% by weight or less, is preferably used in combination. As the alkyl (meth) acrylate, an alkyl (meth) acrylate having an alkyl group having 1 to 12 carbon atoms is preferably used. Specifically, methyl (meth) acrylate,
Ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate,
Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
N-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate and isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, and the like. It is possible to obtain one of these alkyl (meth) acrylates
Species or two or more can be used. In particular, in the present invention, as a radical polymerizable monomer used in the production of the component B, one or more alkyl (meth) acrylates having an alkyl group having 4 to 9 carbon atoms are used as a main component. Is preferred.

As described above, in the production of the component B, together with the alkyl (meth) acrylate,
Other copolymerizable monomers may be used as the minor component. Examples of such “other copolymerizable monomers” include, for example, vinyl aromatic monomers such as styrene, α-methylstyrene, and vinyl toluene; (meth) acrylic acid, crotonic acid,
Unsaturated carboxylic acids such as cinnamic acid, itaconic acid, fumaric acid and maleic acid; monoalkyl esters of unsaturated dicarboxylic acids such as monoethyl itaconate, monobutyl fumarate and monobutyl maleate; (meth) Hydroxyl-containing vinyl monomers such as 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate; (meth) acrylonitrile, vinyl acetate, ( Meta)
Examples thereof include acrylamide, N-methylolacrylamide, glycidyl methacrylate, vinyl acetate, vinyl chloride, and vinylidene chloride. One or more of these copolymerizable monomers can be used.

When the above-mentioned "other copolymerizable monomer" is used, its use ratio is not more than 40% by weight as described above, based on the total weight of the radical polymerizable monomer used for producing the component B. It is preferred that 40% by weight
If it exceeds, sufficient adhesive strength may not be developed after preheating or main heating.

(2-3) Method for Producing Component B As an example of a method for obtaining the component B, a usual emulsion polymerization method using a conventionally known surfactant as an emulsifier can be mentioned. As the surfactant, an anionic surfactant,
Non-ionic surfactants can be used. Also,
Reactive anionic surfactants may be used.

As another method for obtaining the component B, there is a method in which the radical polymerizable monomer used for producing the component B is emulsion-polymerized in the presence of the component A. In this emulsion polymerization method, since the component A functions as a surfactant (emulsifier), the amount of an emulsifier such as a protective colloid or another surfactant used during the emulsion polymerization can be made smaller than in the case of ordinary emulsion polymerization. . Furthermore, if desired, no other emulsifiers can be used. As a result, as compared with the case where the component B is produced by a usual emulsion polymerization method, the anti-blocking property is excellent, and the water resistance and the like of the resin layer can be improved. When the radical polymerizable monomer used for producing the component B is emulsion-polymerized in the presence of the component A, an emulsion containing both the component A and the component B is obtained. Therefore, in this case, the heat-sensitive adhesive composition used in the present invention can be obtained from this emulsion without separately adding the component A, and the production method is most preferable in terms of water resistance and the like. Alternatively, component A may be further added to the emulsion thus obtained.

As the polymerization initiator that can be used in the emulsion polymerization for obtaining the component B, any polymerization initiator generally used in the emulsion polymerization can be used.
Examples of the radical polymerization initiator for obtaining the same include the same organic peroxides, inorganic peroxides, and azo compounds as described above. The preferred amount of the polymerization initiator to be used is 0.1 to 5% by weight based on the total amount of the monomers.

In order to prevent the inside of the system from becoming unstable when the component A is added, the component B is neutralized with a base or the like used for the neutralization of the component A, and the pH of the component A is reduced. pH
It is preferable to keep the distance close to

(3) Component A, B ratio, etc. In the heat-sensitive adhesive composition used in the application method of the present invention,
The weight ratio (solid content ratio) of Component A and Component B is preferably Component A / Component B = 10/90 to 60/40,
More preferably, component A / component B = 25/75 to 50/50. When the content is within the above range, the balance between the tackiness after preheating and / or main heating and the blocking resistance before preheating is improved. The heat-sensitive adhesive composition used in the present invention preferably has a solid concentration of 30 to 70% by weight. If the solid content is less than 30% by weight, the drying property of the composition is insufficient, while if it exceeds 70% by weight, the production becomes difficult and the viscosity of the composition tends to be excessively high. The heat-sensitive adhesive composition used in the present invention is an antifoaming agent usually used for a general adhesive,
Surfactants, fungicides, fragrances, neutralizers, tackifiers, thickeners, leveling regulators, antifreezes, foaming agents, antioxidants, ultraviolet absorbers, reinforcing agents, fillers, pigments, fluorescent It may contain one or more of a whitening agent, an antistatic agent, an anti-blocking agent, a flame retardant, a crosslinking agent, a plasticizer, a lubricant, an organic solvent, a colorant, and the like.

(4) Formation of Resin Layer The material of the sheet base material used in the construction method of the present invention is not particularly limited as long as it can withstand the heating temperature during construction, and is suitable according to the application. You just have to select For example, a sheet base made of cloth, paper, leather, wood, metal, various plastics and the like can be used. Examples of the plastic include polyester, polyamide, vinyl chloride polymer, polyethylene, polypropylene, polyurethane and the like.

The method for applying the heat-sensitive adhesive composition to the surface of the sheet substrate (the surface on the side to be adhered to the adherend) is not particularly limited. For example, roll coater application, spray application, casting application, doctor application Any method such as blade coating and brush coating can be used. Next, the applied heat-sensitive adhesive composition is heated at a temperature at which the heat-sensitive adhesive does not exhibit tackiness to form a resin layer. The coating amount of the resin layer can be appropriately adjusted depending on applications, it is usually about 5g / m ² ~100g / m ² about (preferably 10g / m ² ~50g / m ^2, more preferably about Fifteen
g / m ² ~30g / m ² or so) and it is preferable to. Thereby, the sheet and the adherend can be bonded with sufficient strength.

(II) Construction Operation The material of the adherend used in the construction method of the present invention is:
Any of a wood material, a plastic material, a metal material, and an inorganic material may be used. Examples of wood materials include, in addition to ordinary cut wood, particle board (particle plate), plywood, laminated wood, fiber board (fiber board), and the like. Examples of the plastic material include polypropylene, polyethylene, vinyl chloride, ABS, polystyrene, polyester, polyurethane, acrylic resin, polycarbonate and the like. Examples of the inorganic material include gypsum, concrete, and ceramics. Examples of the metal material include aluminum, iron, and alloys thereof. The shape of the adherend may be a long body or a shape cut into a predetermined shape (for example, a shape previously cut into a square, a circle, an ellipse, or another shape). The adherend may be subjected to surface treatment such as painting or plating.

In the application method of the present invention, the sheet on which the non-adhesive resin layer is formed is preheated to change the resin layer to low adhesion, and the low-adhesion resin layer is used to attach the sheet to the adherend. Temporarily adhere to the surface. At this time, after preheating the entire sheet, the sheet may be disposed on the adherend surface and temporarily bonded, or the sheet before preheating may be preheated after arranging the sheet on the adherend surface. It may be temporarily bonded to the adherend. The resin layer after preheating has low adhesiveness with removability. The term "has removability" means, for example, that a sheet temporarily bonded to an adherend can be peeled without causing elongation or breakage of the sheet base material or adhesive residue on the adherend. Say. Therefore, the sheet after the preliminary heating can be easily peeled off from the surface of the adherend even after the temporary bonding and then re-attached. When the positioning of the sheet is completed using this temporary adhesive property, the temporarily bonded sheet is fully heated to change the resin layer to high adhesiveness, and the sheet is firmly attached to the adherend by the high adhesive resin layer. (Final adhesion). As a heat source for preheating and main heating, a steam iron, a dryer, an infrared dryer, and the like can be used. As the infrared dryer, for example, a product name “POWER” manufactured by Teikoku Piston Ring Co., Ltd.
BOSS ”series or the like may be used.

The sheet before preheating used in the application method of the present invention is laminated and laminated under pressure of 10 g / cm ² for 2 weeks in an atmosphere of 50 ° C., and then stored at 23 ° C. and humidity When left in a 65% atmosphere for 24 hours, when the peel strength of the test piece is measured according to the T peel method specified in ASTM D1876-61T, the peel strength is preferably less than 10 g / 25 mm, preferably 3 g /
More preferably, it is less than 25 mm.

The peel strength of the sheet after preheating on the adherend is 180 as defined in JIS Z 0237.
20 to 300 g / 25 mm (more preferably 100 to 300 g) as the peel strength at a temperature of 25 ° C. by the peeling method
(200 g / 25 mm). Furthermore, for the purpose of performing temporary adhesion and re-attachment for positioning, the sheet after preheating does not leave glue on the adherend in the measurement of the peel strength, and may cause elongation or breakage of the sheet base material. It is preferable to be able to peel off without performing. And the peel strength of the sheet after the main heating to the adherend is
The peel strength at a temperature of 25 ° C. by a 180 ° peeling method specified in JIS Z 0237 is 500 g / 2.
5 mm or more (more preferably 700 g / 25 mm or more)
It is preferable that

(III) Function In the application method of the present invention, a mechanism will be described in which the non-adhesive resin layer changes to a low tackiness having removability by preheating and further changes to a high tackiness by the main heating. . Since the pressure-sensitive adhesive composition used in the present invention is of an aqueous emulsion type, usually, the component A having a hydrophilic portion is located on the outside, and the component B is comprised of particles located on the inside. For this reason, the resin layer formed by drying this composition at "the temperature at which the resin layer does not exhibit tackiness" has a composition in which component A is sea and component B is island, as shown in FIG. Sea-island structure. At this time, since the component A located on the surface of the resin layer is basically a hard resin, the resin layer in this state is non-adhesive and has excellent blocking resistance.

When this non-adhesive resin layer is heated to a certain temperature (adhesion development temperature) or higher, the structure shown in FIG. 1A gradually collapses, and component B appears on the surface of the resin layer. Thereby, the tackiness is gradually increased to a certain value. At this time, the degree of tackiness can be controlled by adjusting the heating temperature and / or the heating time of the resin layer. Specifically, the higher the heating temperature and the longer the heating time, the higher the tackiness tends to be. When the heating is stopped, the change in the sea-island structure of the resin layer is also stopped. Therefore, by heating until the desired adhesiveness is obtained, a low-adhesive resin layer having removability suitable for temporary fixing can be obtained. Thereafter, by heating the sheet again (main heating), the change of the sea-island structure of the resin layer is further advanced, the adhesiveness is improved, and a highly adhesive resin layer can be obtained. This main heating is preferably performed at a temperature higher than the preliminary heating by 10 ° C. or more, preferably by 30 ° C. or more.

As shown in FIG. 1 (b), the resin layer after the main heating has a structure in which the component A is an island and the component B is a sea (that is, the sea-island is reversed when non-adhesive). Construction)
Is particularly preferable since excellent adhesiveness is exhibited. In order to reverse the sea-island as described above, it is preferable that the acid value of the component B is lower than the acid value of the component A by 0.5 meq / g or more (more preferably 1 meq / g or more). Also, the weight ratio of component A to component B (solid content ratio)
Is preferably component A / component B = 10/90 to 60/40 (more preferably 25/85 to 50/50).

The "sea-island structure" described in the present specification is a well-known concept, for example, "New Edition Polymer Dictionary (edited by the Society of Polymer Science, Editing Committee of Polymer Dictionary, published by Asakura Shoten)"
It is described in detail in the section “Sea-island structure” on page 31.
In this specification, “having a sea-island structure” is not limited to a structure in which the sea (continuous layer) is completely continuous and all of the islands (discontinuous layers) are independently dispersed in the sea. The meaning includes a state in which the island is partially interrupted and a state in which a part of the island is fused with each other.

The aqueous emulsion-type heat-sensitive adhesive composition used in the application method of the present invention includes Component A
One type of aqueous emulsion containing the components A and / or B may be used alone, or two or more types of aqueous emulsions having different compositions of the component A and / or the component B may be used in combination. Examples of methods for using two aqueous emulsions include:
A method in which the first aqueous emulsion and the second aqueous emulsion are mixed in advance and applied, a method in which the first aqueous emulsion and the second aqueous emulsion are separately applied in different patterns, and a method in which the first aqueous emulsion is applied. A method in which a second aqueous emulsion is applied over the top, and the like. Also, these methods may be combined.

When two kinds of aqueous emulsions are used in combination as described above, preheating is performed at a temperature at which only particles derived from the first aqueous emulsion exhibit tackiness, and the first and second aqueous emulsions are preliminarily heated. It is preferable to perform the main heating at a temperature at which all of the above exhibit tackiness. At this time, according to the above method, the degree of structural change (sea-island inversion) of the resin layer due to preheating can be adjusted according to the mixing ratio of the first and second aqueous emulsions. The overall tackiness can be controlled. According to the above method, the adhesiveness of the entire resin layer can be controlled by the application area and the application pattern of the first aqueous emulsion that exhibits adhesiveness by preheating. According to the above-mentioned method, for example, the first aqueous emulsion having slightly lower blocking resistance but higher adhesive strength after main heating, and the second aqueous emulsion having higher blocking resistance but slightly lower adhesive strength after main heating. By using in combination with an aqueous emulsion, it is possible to achieve both opposing performances.

[0051]

The present invention will be described more specifically with reference to the following examples and comparative examples. In each of the following examples,
Unless otherwise specified, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively. The abbreviations used below and their contents are shown in Table 1 below. Furthermore, the Tg value of the homopolymer of each monomer used for calculating the Tg of the polymer in this specification is also shown.

[0052]

[Table 1]

(1) Synthesis of Component A (Water-soluble resin A1) In a flask equipped with a stirrer, a condenser, a thermometer and a nitrogen inlet tube, 40 parts of methyl ethyl ketone as a solvent was charged and heated to 75 ° C. Subsequently, BA 18 parts, MMA 5.5 parts, styrene 1 part, MA
A1.5 parts, MPA 2 parts as a chain transfer agent were charged into a flask as initial raw materials, and AIBN was used as a polymerization initiator.
0.5 part was added to initiate the polymerization. Next, BA2
Parts, 49.5 parts of MMA, 9 parts of styrene and MAA1
20 parts of methyl ethyl ketone and 1.0 part of AIBN were mixed and dissolved in 74 parts of 3.5 parts of the mixed solution, and this was dropped into a flask over 4 hours as a continuous raw material to carry out polymerization. After completion of the dropwise addition, 0.5 part of AIBN and 40 parts of methyl ethyl ketone were further charged, and after maintaining at the same temperature for 5 hours, the reaction system was cooled to terminate the polymerization, and the copolymer (acid having a solid content of 50%) was added. (A value of 1.7 meq / g) was obtained. Aqueous ammonia was gradually added to 200 parts of a methyl ethyl ketone solution of the obtained copolymer under stirring to neutralize a carboxyl group in the copolymer to adjust the pH of the reaction solution to about 7 to 8. After that, the temperature 50
The methyl ethyl ketone was removed under reduced pressure at a temperature of ° C. to obtain an aqueous solution A1aq of the water-soluble resin A1 corresponding to the component A.

(Water-soluble resin A2) A water-soluble resin A2 was prepared in the same manner as in the synthesis of the water-soluble resin A1 except that the monomer compositions used for the initial raw material and the continuous raw material were as shown in Table 2.
An aqueous solution A2aq was obtained. For the water-soluble resins A1 and A2, the monomer composition of the entire resin, the ratio of the charged amount of each monomer at each stage of production, the number average molecular weight Mn, the acid value and Tg of the obtained resin, and the aqueous solutions A1aq and A2aq P
Table 2 shows the H and solid content.

[0055]

[Table 2]

(2) Synthesis of heat-sensitive adhesive composition (Adhesive composition 1) Water-soluble resin A1 obtained as described above
In the presence of the above, the radical polymerizable monomer used for the production of the component B was emulsion-polymerized as follows to synthesize an aqueous emulsion-type heat-sensitive adhesive composition. That is, first, 99 parts of BA and 1 part of HEMA were mixed to obtain a monomer mixture. A flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet tube was charged with 80 parts of deionized water and 60 parts of an aqueous solution A1aq of the water-soluble resin A1 (30 parts of an active ingredient), and heated to 60 ° C. under a nitrogen atmosphere. . Thereafter, 10 parts of a 10% aqueous solution of t-butyl hydroperoxide, formaldehyde sodium sulfoxylate dihydrate (trade name “Rongalit C”, manufactured by Iron and Steel Chemical Co., Ltd .;
It is simply called Rongalit. ) 10% aqueous solution 10
And 80 parts of the above monomer mixture were added dropwise over 3 hours. After maintaining the same temperature for 2 hours after the completion of the dropwise addition, the reaction system was cooled to terminate the polymerization, and neutralized with aqueous ammonia to adjust the pH to 7 to 8 to obtain an aqueous emulsion. The solids content of this aqueous emulsion was about 50%.

An anti-blocking agent (a dispersion of olefin fine particles, manufactured by Mitsui Chemicals, Inc., trade name “Chemipearl M-200”, solid content: 40.100 wt. 0%) and 5 parts of a thickener (trade name "K", manufactured by Toagosei Co., Ltd.)
M-36 ", 0.1 part of solid content 30%) and a Brookfield viscosity of 100 mPa (2
The pressure-sensitive adhesive composition 1 was adjusted to 5 ° C., 12 rpm) and pH 7.5.

(Adhesive composition 2) The same amount of aqueous solution A2 of water-soluble resin A2 was used instead of aqueous solution A1aq of water-soluble resin A1.
A pressure-sensitive adhesive composition 2 was obtained in the same manner as in composition 1, except that aq 100 parts (active ingredient 50 parts) was used.

Table 3 shows the types of the components A and B contained in the compositions 1 and 2 and the weight ratio (solid content ratio) thereof together with the liquid property of each composition. All of these compositions correspond to the aqueous emulsion-type heat-sensitive adhesive composition described in the claims.

[0060]

[Table 3]

(3) Formation of Resin Layer (Sheet 1, 2) The adhesive composition 1 was applied to a vinyl chloride sheet for wallpaper as a sheet base material, and the coated amount after drying was about 15 g.
/ M ^2, and dried by a hot air drier at 50 ° C. for 3 minutes to obtain Sheet 1. Further, the pressure-sensitive adhesive composition 2 was similarly applied to the above-mentioned sheet substrate and dried to obtain a sheet 2.

(Sheet 3) The pressure-sensitive adhesive composition 1 was spray-coated on the sheet substrate so that the coating amount after drying was about 10 g / m ^2, and dried at 50 ° C. for 2 minutes using a hot-air drier. . Next, the pressure-sensitive adhesive composition 2 is spray-coated on the pressure-sensitive adhesive layer formed from the composition 1 so that the coating amount after drying becomes about 5 g / m ² , and the pressure-sensitive adhesive is dried at 50 ° C. by a hot air drier.
After drying for 3 minutes, Sheet 3 was obtained. The resin layer of the sheet 3 has a configuration in which the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition 2 is provided on the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition 1.

(Sheet 4) A commercially available delate tack-type adhesive comprising dicyclohexyl phthalate as a crystalline plasticizer, a rosin ester-based resin as a tackifier, and a vinyl-based resin as a resin binder (Toyo Ink Manufacturing Co., Ltd.) Sheet No. 4 (product name: BPW-5249, solid content: 52%) was applied and dried in the same manner as sheet 1.

(4) Evaluation of workability For the sheets 1 to 4 on which the resin layer was formed, the adhesive strength after preliminary heating (temporary adhesion), the adhesive strength after final heating (final adhesion), and the storage time Was evaluated for the blocking resistance by the following methods. Table 4 shows the results.

Temporary adhesiveness A test piece was obtained by cutting each sheet to a width of 25 mm and a length of about 250 mm. The test piece was heated using a steam iron (manufactured by Toshiba Corp., model name “TA-610S”, scale) with a surface temperature of about 80 ° C., and the adherend [using a medium density fiber board (MDF board)] Was lightly pressed. Next, the sample was allowed to stand for 15 minutes in an atmosphere at a temperature of 23 ° C. and a humidity of 65%, and then the adhesive strength of the test piece was measured according to a 180 ° peeling method specified in JIS Z 0237. That is, in an atmosphere of a temperature of 23 ° C. and a humidity of 65%, the 180-degree peeling strength of the adherend was measured at a tensile speed of 200 mm / min. The measurement results are shown in the following two stages. ：: peel strength of 20 g / 25 mm or more, 300 g / 25 m
less than m. The test piece could be peeled off without leaving adhesive on the adherend. Good temporary fixability. X: Peel strength of 300 g / 25 mm or more, or adhesive residue on the adherend occurred. There is a problem with temporary fixing.

Main Adhesiveness A test piece was obtained by cutting each sheet to a width of 25 mm and a length of about 250 mm. The test piece was heated using a steam iron (manufactured by Toshiba Corporation, model name “TA-610S”, scale) having a surface temperature of about 130 ° C., and lightly pressed to the adherend. Next, the sample was allowed to stand for 15 minutes in an atmosphere at a temperature of 23 ° C. and a humidity of 65%, and then the adhesive strength of the test piece was measured according to the 180 ° peeling method specified in JISZ0237. That is, in an atmosphere of a temperature of 23 ° C. and a humidity of 65%, the 180-degree peeling strength of the adherend was measured at a tensile speed of 200 mm / min. The measurement results are shown in the following three stages. ：: peel strength of 700 g / 25 mm or more. Δ: Peel strength of 500 g / 25 mm or more, 700 g / 25
less than mm. X: Peel strength less than 500 g / 25 mm.

Blocking Resistance Each sheet was cut to a width of 25 mm and a length of about 250 mm to obtain a test piece. This test piece was combined with a sheet substrate on which the resin layer was not formed (corresponding to a state in which the sheets having the resin layer formed were stacked or wound).
The pressure was increased to 10 g / cm ² in an atmosphere at a temperature of 50 ° C. for 2 weeks. Next, 24 hours in an atmosphere of 23 ° C. and 65% humidity.
After standing for a period of time, the peel strength of the test piece was measured according to the T peel method specified in ASTM D1876-61T. The measurement results are shown in the following three stages. A: Peel strength less than 3 g / 25 mm. Particularly excellent in blocking resistance. ：: Peel strength of 3 g / 25 mm or more and less than 10 g / 25 mm. Has some blocking properties, but no problem in practical use. X: Peel strength of 10 g / 25 mm or more. Blocking is seen and there is a practical problem.

[0068]

[Table 4]

As shown in Table 4, according to Embodiments 1 to 3 which are the construction methods of the present invention, the sheet after preheating is temporarily fixed, and the position is corrected by peeling off the temporarily fixed sheet as necessary. After the positioning is completed, the permanent bonding can be performed. The sheet used in the construction method of the present invention is different from a sheet using a conventional re-wet sheet or a hot-melt type adhesive, because the tackiness caused by preheating does not substantially change with time, and thus the time required for positioning. Is not constrained. On the other hand, if the main heating is performed, high tackiness is immediately expressed,
The time from the end of positioning to the actual bonding can be reduced. Further, all of the sheets used in Examples 1 to 3 have good blocking resistance, and can be stored in a stacked state without using release paper or the like.

On the other hand, in Comparative Example 1 using the conventional derate tack type adhesive, the adhesive softened and the adherend (MD
The phenomenon of adhesive residue on the F board) was observed, and the temporary adhesion was poor.

[0071]

According to the application method of the present invention, a non-adhesive resin layer formed from a specific aqueous emulsion-type heat-sensitive adhesive composition is temporarily adhered to an adherend with low tackiness by preheating, Next, the resin layer is made to have high tackiness by main heating, and is permanently bonded to the adherend. At the time of the temporary bonding, it is possible to repeatedly perform operations such as peeling off the temporarily fixed sheet as needed and correcting the position without any time limitation. Further, since the resin layer before preheating has excellent blocking resistance, the sheet on which the resin layer is formed can be stored in a stacked or wound state without using a release paper or the like.

[Brief description of the drawings]

FIG. 1A is a schematic diagram illustrating a cross-sectional structure of a resin layer according to the present invention before preheating, and FIG. 1B is a schematic diagram illustrating a preferable cross-sectional structure after main heating.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Hiroshi Iesako 1 of Funami-cho, Minato-ku, Nagoya-shi, Aichi F-term in Nagoya Research Laboratory, Toagosei Co., Ltd. 4F100 AK01B AK12 AK12J AK25 AK25J AL01 AL05B AT00A BA02 DG10A EC182 EJ422 GB81 GB90 JA05B JB05B JK06 JL13B YY00 YY00B 4J004 AA07 AA10 AB01 AB03 CA02 CA04 CA06 CA08 CB01 CB02 CC02 4J040 DA051 DA052 DB031 DB032 DB081 DB082 DE031 DE032 DF04 PA01 GA12

Claims (3)

[Claims] 1. A sheet having a resin layer formed by the following method is preheated and temporarily adhered to an adherend surface, and then the sheet is fully heated and the sheet is permanently adhered to the adherend. A method of applying a sheet, wherein the resin layer is non-adhesive before the preheating, has low tackiness with removability after the preheating, and has high tackiness after the main heating. A sheet construction method, characterized in that: [Method of Forming Resin Layer] (A) A hydrophilic portion is provided on the surface of the sheet substrate, and the glass transition temperature of the hydrophilic portion is 20 ° C.
An aqueous emulsion type heat-sensitive adhesive composition comprising the above water-soluble resin and (B) a polymer having a glass transition temperature of −20 ° C. or lower obtained by emulsion polymerization of a radical polymerizable monomer is applied. Then, the heat-sensitive adhesive is dried at a temperature not higher than the temperature at which the heat-sensitive adhesive is developed. 2. The sheet before the preheating is AST
The peel strength at a temperature of 25 ° C. by the T peel method specified in MD1876-61T is 10 g / 25 mm or less, and the sheet after the preheating is JIS Z 0237.
The peel strength at a temperature of 25 ° C. according to the 180 ° peeling method specified in the above is in the range of 20 to 300 g / 25 mm, and the sheet after the main heating is a temperature of 25 ° C. according to the 180 ° peeling method specified in JIS Z 0237. 2. The method according to claim 1, wherein the peel strength of the sheet is 500 g / 25 mm or more. 3. The method according to claim 1, wherein the sheet is fusuma paper or wallpaper.