TWI597303B - Curable resin composition, adhesive layer-equipped transparent surface material, and laminate - Google Patents

Description

Curable resin composition, transparent surface material with adhesive layer and laminate Field of invention

The present invention relates to a curable resin composition, a transparent surface material with an adhesive layer, and a laminate.

Background of the invention

As a method of using a laminate having an adhesive layer between a pair of face materials, a display device in which a protective sheet is bonded to the surface of a display panel via an adhesive layer is known. As a method of producing the laminated body, a transparent surface material in which an adhesive layer is formed on the surface of the surface material to be a protective sheet in advance, and the transparent surface material of the adhesive layer is to be used as a display panel The face material is bonded in such a manner that the adhesive layer is in contact with the display panel.

It is known that the adhesive layer of the transparent surface material and the laminated body with the adhesive layer has a layer portion extending along the surface of the surface material and a weir portion surrounding the periphery of the layer portion, and the layer portion is made of hardenability. The compound and the cured product of the curable resin composition of the non-curable oligomer are composed (see Patent Documents 1 and 2).

For example, the display panel and the pre-manufactured adhesive layer In the method of bonding a transparent surface material, there is a method of laminating a display panel and a transparent surface material with an adhesive layer in a reduced pressure atmosphere to return it to an atmospheric pressure environment. When the display panel is bonded to the transparent surface material with the adhesive layer in a reduced-pressure atmosphere, a gap is formed at the interface between the display panel and the adhesive layer. However, when the bonded display panel and the transparent surface material with the adhesive layer are returned to the atmospheric pressure environment, the pressure in the gap (maintaining the pressure reduction) and the pressure applied to the adhesive layer (atmospheric pressure) are differential pressure. , the volume of the gap can be reduced, and the void disappears.

In another method of obtaining a laminate, a method of coating an unhardened resin composition to be an adhesive layer on a face material, and then laminating a face material to be a display panel to harden the adhesive layer to obtain a laminate is obtained.

When the curable resin composition forming the layered portion contains a non-curable oligomer which does not participate in the curing reaction, the fluidity of the formed layer portion is compared with the case where the non-curable oligomer is not contained. Increase. Therefore, the cured product forming the layered portion is liable to flow into the gap, so that the void which has been formed at the interface between the adhesive layer and the display panel at the time of bonding can disappear in a short time.

Further, the non-curable oligomer is included to make the layered portion of the adhesive layer low in elasticity. Therefore, the stress applied to the display panel which has been bonded to the above-mentioned adhesive layer is small, and display unevenness of the display device can be suppressed.

Prior technical literature Patent literature

Patent Document 1: International Publication No. 2011/158839

Patent Document 2: International Publication No. 2012/077726

Summary of invention

However, after the adhesive layer of the laminated body or the transparent surface material with the adhesive layer is formed, once a predetermined time elapses in a room temperature or a high temperature environment, there is an adhesive layer corresponding to a boundary region between the layer portion and the beak portion. At the interface between the bonded display panel and the adhesive layer, a problem of poor bonding such as voids or the like remains.

The present invention provides a curable resin composition for forming a layered portion, which can reduce stress applied to hardening shrinkage of a face material, and can form an adhesive layer even after a predetermined time has elapsed. It is still difficult to produce a transparent surface material and a laminate having an adhesive layer in which a joint defect such as a void remains in the interface between the face material and the adhesive layer such as the bonded display panel. Moreover, the present invention provides a transparent surface material and a laminate having an adhesive layer formed using the curable resin composition.

The inventors of the present invention have conducted detailed studies on the problems of the above-described joint failure, and found that the following matters are the main causes. Specifically, the difference in concentration between the non-curable oligomers between the layered portion and the adhesive layer of the beak portion causes the non-curable oligomer to diffuse from the layer portion to the weir portion as time passes. As a result, at the interface between the layered portion and the weir portion, the volume of the weir portion is increased and expanded, and the volume of the layer portion is reduced, so that the surface of the layer portion becomes concave and the surface of the weir portion becomes convex. There is a step difference on the surface of the adhesive layer. As a result, when it is bonded to a face material such as a display panel, the interface between the adhesive layer and the display panel is caused to occur at a portion corresponding to the interface between the layered portion and the beak portion. There is a poor bonding of the gap or the like.

Further, the present invention and the like have been found to be a curable resin composition for forming a layered portion by using a curable resin composition containing an oligomer (C) having an average number of curable functional groups of 0.5 to 1. The same effect as that of the non-hardening oligomer can be obtained, and even after a predetermined time elapses after the formation of the adhesive layer, voids can be suppressed from occurring at the interface between the adhered adhesive layer and the face material.

The curable resin composition of the present invention is for forming a layered portion in an adhesive layer which is an adhesive layer which bonds a pair of face materials, and has a layered portion which spreads along the surface of the face material and surrounds the aforementioned a weir-like portion around the periphery of the layered portion; the curable resin composition contains the following oligomer (A), the following monomer (B), and the following oligomer (C): oligomer (A): An oligomer having a number average molecular weight of 1,000 to 100,000 and an average number of hardening functional groups of 1.8 to 4; a monomer (B): at least one type having a molecular weight of 125 to 600 and a hardening functional group of 1 to 3 A monomer comprising at least one monomer having a hydroxyl group (B1).

Oligomer (C): an oligomer having a number average molecular weight of 1,000 to 20,000 and an average number of hardening functional groups of 0.5 to 1.

The curable resin composition of the present invention preferably contains a photopolymerization initiator (E1).

Further, the curable resin composition of the present invention further contains the following non-curable oligomer (D): a non-curable oligomer (D): not bonded to the oligomer (A) or monomer at the time of curing (B) and the oligomer (C) undergo a hardening reaction and have a hydroxyl group, each hydroxyl group An oligomer having a molecular weight of 400 to 8,000.

In addition, the ratio of the oligomer (C) is preferably from 50 to 100% by mass based on the total of the oligomer (C) and the non-curable oligomer (D) (100% by mass).

Further, the curable functional group is preferably an acryloxy group or a methacryloxy group.

Further, the oligomer (A) is preferably one in which a polyol and a polyisocyanate are reacted to obtain a prepolymer having an isocyanate group at the terminal, and then the following monomer (a1) is reacted with the isocyanate group of the prepolymer. The obtained urethane acrylate oligomer; and the oligomer (C) is preferably a monomer obtained by reacting a unit alcohol with a polyisocyanate to obtain an isocyanate group having only one terminal end. C1) an oligomer obtained by reacting an isocyanate group of the prepolymer.

Monomer (a1): a monomer having a molecular weight of from 125 to 600, having one or more acryloxy groups and having one reactive group with an isocyanate group.

Monomer (c1): a monomer having a molecular weight of from 125 to 600, having one or more acryloxy groups and having one reactive group with an isocyanate group.

In addition, the oligomer (A) is preferably 6 to 80% by mass based on the total of the oligomer (A), the monomer (B), and the oligomer (C) (100% by mass), and the monomer (B) is preferably from 3 to 70% by mass, and the oligomer (C) is preferably from 10 to 70% by mass.

The transparent surface material with an adhesive layer of the present invention has a transparent surface material and an adhesive layer provided on the surface of the transparent surface material, and the adhesive layer has a layered portion extending along the surface of the transparent surface material and surrounding the periphery of the layered portion. Braid The layered portion is composed of a cured product of the curable resin composition of the present invention.

The laminated body of the present invention has: a pair of face materials; and an adhesive layer provided between the face materials and the two faces facing each other; the adhesive layer has a layered portion extending along the surface of the face material and surrounding The weir-like portion of the peripheral edge of the layered portion; the layered portion is composed of a cured product of the curable resin composition of the present invention.

The curable resin composition of the present invention and the obtained transparent surface material or laminate of the adhesive layer can reduce the stress applied to the face material, and it is difficult to display the bonded surface even after a predetermined time after the formation of the adhesive layer. A joint failure such as a void or the like remaining in the interface between the face material such as the panel and the adhesive layer occurs.

1‧‧‧Transparent surface material with adhesive layer

10‧‧‧Transparent surface material

12‧‧‧Lighting Printing Department

14‧‧‧Adhesive layer

16‧‧‧Protective film

18‧‧‧Layered

20‧‧‧堰

Fig. 1 is a cross-sectional view showing an example of a transparent face material with an adhesive layer of the present invention.

Form for implementing the invention

In the present specification, "transparent" means that the surface material and the display surface of the display panel are bonded together without a gap through the adhesive layer, and the whole or a part of the display image of the display panel can be visually transmitted through the surface material without being optically strained. state. Therefore, even if a part of the light incident from the display panel to the face material is absorbed or reflected by the face material, or the visible light transmittance of the face material is reduced due to an optical phase change or the like, the display of the display panel can be visually observed without optical strain of the face material. The imager can be called "transparent".

Moreover, the "curable functional group" means a functional group having a radical polymerizable unsaturated bond. Further, "(meth) acrylate" is a generic term for acrylate and methacrylate.

Further, the average number of the curable functional groups of the oligomer indicates the average number of the curable functional groups per molecule of the oligomer 1 molar. The average number of hardening functional groups of the oligomer can be calculated from the blending of the raw materials in the production of the oligomer.

The number average molecular weight of the oligomer in the present invention is a polystyrene-converted number average molecular weight obtained by gel permeation chromatography (GPC). On the other hand, when a spike of an unreacted low molecular weight component (monomer or the like) occurs in the GPC measurement, the number average molecular weight is calculated by subtracting the peak.

≪hardenable resin composition≫

The curable resin composition of the present invention is a curable resin composition for forming a layered portion of an adhesive layer which is an adhesive layer which bonds a pair of face materials and has a layered shape extending along the surface of the face material. a portion and a weir portion surrounding the periphery of the layered portion. Hereinafter, the curable resin composition for forming the layered portion is referred to as the first composition, and the curable resin composition for forming the beak portion is referred to as the second composition.

The first composition in the present invention is a composition of an oligomer (A), a monomer (B), and an oligomer (C) which will be described later as essential components.

The first composition may be a photocurable resin composition or a thermosetting resin composition. As the first composition, a photocurable resin composition further blended with the photopolymerization initiator (E1) is preferred from the viewpoint of being hardenable at a low temperature and having a high curing rate. Further, the first composition is a photocurable resin composition, that is, it does not require high temperature for hardening, so there is also a low temperature. This causes damage to the display panel and the like.

Further, it is preferred that the first composition is further blended with a non-curable oligomer (D). Further, the first composition may be blended with an additive as needed.

(oligomer (A))

The oligomer (A) has an average molecular weight of 1,000 to 100,000 and an average of the hardening functional groups of 1.8 to 4.

The oligomer (A) preferably has two or more and four or more curable functional groups in one molecule, and in the oligomer (A) production step, an oligomer having a desired number of curable functional groups is formed. The case of by-products other than the object. The number of the curable functional groups of the oligomer (A) is from 1.8 to 4 in the case of also containing the by-product.

The oligomer (A) has a number average molecular weight of 1,000 to 100,000, preferably 10,000 to 70,000. When the number average molecular weight of the oligomer (A) is in the above range, the viscosity of the first composition is easily adjusted to the above range, and a cured film having no bubble residue can be easily obtained.

As the curable functional group of the oligomer (A), an acryloxy group or a methacryloxy group is preferred, and an acryloxy group is particularly preferred.

The average number of the curable functional groups of the oligomer (A) is from 1.8 to 4, and preferably from 1.8 to 3, from the viewpoint of the curability of the first composition and the mechanical properties of the layer portion.

The oligomer (A) may be one type or two or more types.

As the oligomer (A), an urethane oligomer is preferred, and the following oligomer (A1) is particularly preferred.

Oligomer (A1): reacting a polyol with a polyisocyanate to obtain an end After the prepolymer having an isocyanate group, an urethane acrylate oligomer obtained by reacting the following monomer (a1) with an isocyanate group of the prepolymer is used.

Monomer (a1): a monomer having a molecular weight of from 125 to 600, having one or more acryloxy groups and having one reactive group with an isocyanate group.

The monomer (a1) may, for example, be a monomer having a reactive hydrogen group (hydroxyl group, an amine group or the like) and an acryloxy group.

Specific examples of the monomer (a1) include a hydroxyalkyl acrylate having a hydroxyalkyl group having 2 to 6 carbon atoms (2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate). , 4-hydroxybutyl acrylate, etc.).

As the monomer (a1) which reacts with the above prepolymer, a hydroxyalkyl acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms is preferred.

As the polyol and the polyisocyanate, a known compound can be used, and for example, the polyol (i) and the diisocyanate described in the raw material of the urethane-based oligomer (a) in International Publication No. 2009/016943 can be used. Ii) Wait. That is, the polyol (i) having an average of 1.8 to 4 hydroxyl groups per molecule and the diisocyanate diisocyanate (ii).

The oligomer (A) having an average number of the curable functional groups in the above range can be obtained by adjusting the raw material blend ratio at the time of producing the oligomer (A). For example, in the case of the oligomer (A1), it can be obtained by the following method.

(i) an oligomer having an average of 1.8 to 2 hardening functional groups (A1)

In the method, an average of 1.8 to 2 functional polyols and a bifunctional polyisocyanate are reacted to obtain a prepolymer having an average of 1.8 to 2 isocyanate groups at the terminal, and then 1 molecule has a curable functional group and 1 hydroxyl group. Monomer (a11) The reaction was carried out so that the isocyanate group/hydroxyl molar ratio became 1/1.

(ii) an oligomer having an average of 2 to 4 hardening functional groups (A1)

In the method, an average of a bifunctional polyol and a bifunctional polyisocyanate are reacted to obtain a prepolymer having an average of two isocyanate groups at the terminal, and a single hydroxyl group and one or more hardening functional groups in one molecule are obtained. The body (a12) is reacted so that the isocyanate group/hydroxyl molar ratio is 1/1 and the curable functional group is 2 to 4 on average.

Specific examples of the polyhydric alcohol include polyoxyalkylene polyols (polyoxyethylene glycol, polyoxypropylene propylene polyol, etc.), polyester polyols, and polycarbonate polyols. Among these, as the polyol, a polyoxyalkylene polyol is preferred, and a polyoxypropylene propylene polyol is preferred. Further, it is more preferable to use a polyoxyalkylene polyol having an oxygen-extended alkyl group having an oxygen-extended propyl group and an oxygen-extended ethyl group to improve compatibility between the first composition and other components. Further, in the case of a polyoxyalkylene polyol, a cured product having high flexibility can be easily obtained even in a low temperature region, and in particular, a polyoxyalkylene polyol composed of an oxygen-extended ethyl group and an oxygen-extended propyl group is good.

The polyhydric alcohol may be one type or two or more types.

The polyisocyanate is preferably at least one diisocyanate selected from the group consisting of aliphatic diisocyanates, alicyclic diisocyanates, and non-yellowing aromatic diisocyanates.

Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, and 2,4,4-trimethyl-hexamethylene diisocyanate. .

As the alicyclic polyisocyanate, isophorone diisocyanate can be mentioned, Methylene bis(4-cyclohexyl isocyanate) and the like.

The non-yellowing aromatic diisocyanate may, for example, be xylene diisocyanate.

The polyisocyanate may be one type or two or more types.

The ratio of the oligomer (A) is preferably 20 to 90% by mass, and 30 to 80% by mass based on the total of the oligomer (A) and the monomer (B) in the first composition (100% by mass). % is better. When the ratio of the oligomer (A) is at least the lower limit value, the heat resistance of the layer portion is good. When the ratio of the oligomer (A) is at most the upper limit, the curability of the first composition and the adhesion between the face material and the layer portion are preferable.

(monomer (B))

The monomer (B) is a monomer composed of at least one monomer having a molecular weight of 125 to 600 and a number of curable functional groups of 1 to 3, and containing at least one monomer (B1) having a hydroxyl group. By containing the monomer (B1), good adhesion between the face material and the layered portion can be obtained.

The hydroxyl group derived from the monomer (B) remains in the layered portion composed of the cured product of the first composition. When the non-curable oligomer (D) described later is blended in the first composition, the presence of the hydroxyl group contributes to the dispersion stabilization of the non-curable oligomer (D) in the layer portion.

The molecular weight of the monomer (B) is from 125 to 600, preferably from 140 to 400. The smaller the molecular weight of the monomer (B), the better the adhesion between the face material and the layer portion. When the molecular weight of the monomer (B) is at least the lower limit value, the volatilization of the monomer (B) can be suppressed when the transparent surface material or the laminate having the adhesive layer is produced by the method described later.

The monomer (B) may be one type or two or more types.

The number of the curable functional groups of the monomer (B) is from 1 to 3, preferably from 1 to 2. As the monomer (B), it is preferred to use a monomer having one curable functional group and two or more monomers having a curable functional group.

The hardening functional group of the monomer (B) may, for example, be an acryloxy group or a methacryloxy group. The curable functional group of the monomer (B) is preferably an acryloxy group or a methacryloxy group from the viewpoint of a fast curing rate and a layer portion having high transparency; From the viewpoint of obtaining a difference in reactivity between the oligomer (A) and the curable functional group of the monomer (B) and a homogeneous layered portion, it is particularly preferable to use a methacryloxy group.

The monomer (B1) preferably has 1 or 2 hydroxyl groups.

Examples of the monomer (B1) having one hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. Base) 4-hydroxybutyl acrylate, 6-hydroxyhexyl methacrylate, and the like.

Examples of the monomer (B1) having two hydroxyl groups include glycerin monomethacrylate and 2,3-dihydroxypropyl acrylate.

As the monomer (B1), a hydroxy methacrylate having a hydroxyl group of 1 to 2 and a carbon number of 3 to 8 (2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, A) Preferably, 4-hydroxybutyl acrylate or the like is preferred, and 2-hydroxybutyl methacrylate is preferred.

The monomer (B1) may be one type or two or more types.

The curable resin composition of the present invention may further contain the following monomer (B2).

Monomer (B2): has 1 to 3 hardening functional groups and has a molecular weight of 125~ 600 and no hydroxyl monomer.

As the monomer (B2), the following monomer (B21) is preferred. When the monomer (B21) content is more than the monomer (B1) content by mass ratio, the bonded surface material such as a display panel and the transparent surface material of the adhesive layer are bonded to each other in a reduced-pressure atmosphere, and then restored to In an atmospheric pressure environment, there is a tendency to shorten the time until the void of the adhesive layer disappears. On the other hand, if the monomer (B21) is contained, the time required for the first composition to harden tends to increase.

Monomer (B21): an alkyl methacrylate having no hydroxyl group and having an alkyl group having 8 to 22 carbon atoms.

Examples of the monomer (B21) include n-dodecyl methacrylate, n-octadecyl methacrylate, and benzalkonium methacrylate. As the monomer (B21), n-dodecyl methacrylate or n-octadecyl methacrylate is preferred.

The monomer (B2) may be one type or two or more types.

The ratio of the monomer (B) is preferably from 10 to 80% by mass, and from 20 to 70% by mass based on the total of the oligomer (A) and the monomer (B) in the first composition (100% by mass). Preferably.

The ratio of the monomer (B1) is preferably from 10 to 60% by mass, and from 20 to 50% by mass based on the total of the oligomer (A) and the monomer (B) in the first composition (100% by mass). Preferably. When the ratio of the monomer (B1) is at least the lower limit value, the storage stability of the first composition and the adhesion between the surface material and the layer portion are excellent.

The ratio of the monomer (B2) is preferably from 10 to 50% by mass, and from 20 to 40% by mass based on the total of the oligomer (A) and the monomer (B) in the first composition (100% by mass). Preferably. When the ratio of the monomer (B2) is at least the lower limit value, it is easy to sufficiently obtain the effect of adding the monomer (B2).

However, in the synthesis of the oligomer (A1), the monomer (a1) which has reacted with the isocyanate group of the prepolymer is partially present as one of the oligomers (A), and thus is not contained in the first composition. In the ratio of monomer (B). On the other hand, in the synthesis of the oligomer (A1), a monomer which is a diluent (which does not react with the prepolymer) is added to the oligomer (A1) during synthesis or after the synthesis, and is equivalent to the monomer ( In the case of B), the monomer is also contained in the ratio of the monomer (B) in the first composition.

The treatment of the monomers used in the synthesis of the oligomer (C) is also the same.

(oligomer (C))

The oligomer (C) has an average molecular weight of 1,000 to 20,000 and an average of 0.5 to 1 of the curable functional groups.

The oligomer (C) has a number average molecular weight of 1,000 to 20,000, preferably 2,000 to 10,000. When the number average molecular weight of the oligomer (C) is within this range, the viscosity of the first composition is easily adjusted to the above range.

The blending of the oligomer (C) in the first composition contributes to shortening the time required for the voids formed at the interface between the adhesive layer and the display panel to be lost when bonding to a display panel or the like, or to assist in suppressing the attachment. The display surface of the transparent surface material of the adhesive layer and the display panel is not uniform.

Examples of the curable functional group of the oligomer (C) include an acryloxy group and a methacryloxy group. The curable functional group of the oligomer (C) is preferably an acryloxy group or a methacryloxy group from the viewpoint of a fast curing rate and a layer portion having high transparency; From the viewpoint of obtaining a layered portion in which the difference in reactivity between the oligomer (C) and the hardenable functional group of the monomer (B) is small and homogeneous, it is particularly preferable to use an acryloxy group.

From the viewpoint of the hardenability of the first composition and the mechanical properties of the layered portion It appears that the average number of the curable functional groups of the oligomer (C) is from 0.5 to 1, preferably from 0.7 to 1. When the number of the curable functional groups exceeds 1, the crosslinkable oligomer is obtained, and the elastic modulus of the cured product of the curable resin composition is easily increased, so that it is applied to the display panel which has been bonded to the adhesive layer. The stress is increased to make the display device prone to display unevenness. Further, the layered portion loses fluidity, and the void which has been formed at the interface between the adhesive layer and the display panel at the time of bonding tends to remain. Therefore, it is preferred to select a raw material for producing the oligomer (C) so as not to contain more than one reaction product.

As the oligomer (C), the following oligomer (C1) is preferred.

Oligomer (C1): a hardening obtained by reacting a unit alcohol with a polyisocyanate to obtain a prepolymer having an isocyanate group at only one terminal, and reacting the following monomer (c1) with an isocyanate group of the prepolymer. A polyurethane monoacrylate oligomer having an average number of functional groups of 0.5 to 1.

Monomer (c1): a monomer having a molecular weight of from 125 to 600, having one or more acryloxy groups and having one reactive group with an isocyanate group.

The average number of the curable functional groups of the oligomer (C) can be controlled to 0.5 to 1 by adjusting the raw material blend ratio at the time of producing the oligomer (C).

For example, it can be produced by the following method.

In the method (iii), the monool and the diisocyanate are reacted at a ratio of the isocyanate group/hydroxyl molar ratio of 1.0 to 2.0 to obtain a prepolymer having an average of 0.5 to 1.0 isocyanate groups per molecule. The isocyanate group of the prepolymer and the monomer (c11) having one propylene decyloxy group are reacted such that the isocyanate group/isocyanate group and the molar ratio of the reacting group are 1/1.

The method (iv) is carried out by reacting a unit alcohol with a compound having one each of an acryloxy group and an isocyanate group in one molecule at a ratio of an isocyanate group/hydroxyl group having a molar ratio of from 0.5 to 1.0, thereby obtaining one molecule. An average of 0.5 to 1.0 propylene oxime compounds.

The above-mentioned polyol and polyisocyanate used in the oligomer (C) may be the same as those exemplified in the above oligomer (A1), and preferred embodiments are also the same. Further, the monomer (c1) may be the same as the above-mentioned monomer (a1), and the preferred embodiment is also the same.

The oligomer (C) may be one type or two or more types.

In the present invention, the oligomer (A) and the oligomer (from the viewpoint of the state in which the first composition before the hardening can be stabilized and the separation of the oligomer (C) from the layered portion after the hardening are observed. C) Molecular chains of the same structure or similar structure are preferred. In the present invention, it is preferred that the oligomer (A) is an oligomer (A1) and the oligomer (C) is an oligomer (C1).

The ratio of the oligomer (C) in the first composition (100% by mass) is preferably from 10 to 70% by mass. When the ratio of the oligomer (C) is at least the lower limit value, it is difficult to leave a void between the layer portion and the face material. When the ratio of the oligomer (C) is at most the upper limit value, the curability of the first composition and the adhesion between the face material and the layer portion are preferable.

(non-hardening oligomer (D))

The non-hardening oligomer (D) does not undergo a hardening reaction with the oligomer (A), the monomer (B), and the oligomer (C), and has a hydroxyl group, and each of the hydroxyl groups has a molecular weight of 400 to 8,000. Oligomer.

When the first composition contains the non-curable oligomer (D), the fluidity of the first composition is improved, and the elastic modulus of the layered portion can be reduced. So, not hard The chemical oligomer (D) helps to shorten the formed surface to be bonded when the transparent surface material with the adhesive layer is bonded to the bonded surface material in a reduced pressure atmosphere and then returned to the atmospheric pressure environment. The time required for the void at the interface between the material and the adhesive layer to disappear. Further, the non-curable oligomer (D) suppresses application of the first composition to the surface material to form an uncured layer portion, and then further deposits the layer material on the uncured layer portion in a reduced-pressure atmosphere. And returning to the stress applied to the face material when the uncured layer is hardened under atmospheric pressure. The non-hardening oligomer (D) is easily obtained in a small amount, but when it is formed into a layered portion, it diffuses to the ridge portion, which may cause deformation (step difference) at the interface between the layer portion and the ridge portion. When the liquid crystal display is attached to the main cause of voids or residual, it is preferable to use it within the range of the amount described later.

The average number of hydroxyl groups of the non-curable oligomer (D) is preferably 0.8 to 3, and preferably 1.8 to 2.3.

The number average molecular weight per one hydroxyl group of the non-curable oligomer (D) is from 400 to 8,000. When the number average molecular weight per one hydroxyl group is 400 or more, the polarity of the non-curable oligomer (D) does not become too high, and the oligomer (A), the monomer (B), and the oligomer ( C) It is easy to obtain good compatibility. When the number average molecular weight per one hydroxyl group is 8,000 or less, it is easy to obtain non-hardening oligomerization by the interaction between the hydroxyl group derived from the monomer (B1) and the hydroxyl group of the non-hardenable oligomer (D). The effect of the substance (D) being stably dispersed in the layered portion after hardening. This interaction is presumed to be related to hydrogen bonding.

The non-curable oligomer (D) may be one type or two or more types.

The non-curable oligomer (D) may, for example, be a high molecular weight polyol. As a non-hardening oligomer (D), a polyoxyalkylene polyol, Polyester polyols and polycarbonate polyols are preferred. Further, when the oligomer (A) is a urethane acrylate using a polyoxyalkylene polyol as a raw material, the non-curable oligomer (D) is a polyoxyalkylene group in order to improve compatibility. Polyols are preferred.

The polyoxyalkylene polyol may, for example, be a polyoxyalkylene glycol such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxypropylene glycerol or polyoxybutylene glycol.

The polyoxyalkylene polyol has a number average molecular weight of from 400 to 8,000 per one hydroxyl group, preferably from 600 to 5,000.

The number average molecular weight of the non-curable oligomer (D) is determined by the hydroxyl value P (mgKOH/g) and the non-hardening oligomer (D) measured according to JIS K 1557-1 (2007 edition). The average number of hydroxyl groups Q of the molecule is a value calculated by the following formula (1).

Molecular weight of non-hardening oligomer (D) = 56.1 × Q × 1000 / P... (1)

From the viewpoint that the elastic modulus of the layered portion after hardening is more likely to be lower, it is preferred to use a polyoxyalkylene polyol as the non-curable oligomer (D), particularly preferably a polyoxy-extension propylene polyol. Further, as the non-curable oligomer (D), a polyoxyalkylene polyol having an oxygen-extended propyl group and an oxygen-extended ethyl group can also be used.

Further, in the present invention, the oligomer (A) is obtained from the viewpoint of stabilizing the mixed state of the first composition before curing and suppressing separation of the non-curable oligomer (D) from the layered portion after hardening. Or the oligomer (C) and the non-hardening oligomer (D) preferably have a molecular chain of the same structure or a similar structure.

Specifically, as the raw material of the oligomer (A) or the oligomer (C) in the first composition, a compound having a hydroxyl group (hereinafter referred to as "hydroxyl-containing compound") is preferably used, and the same hydroxyl group is used. Non-hardening oligomerization The object (D) is preferred.

In the first composition, the oligomer (A) or the oligomer (C) is an urethane acrylate oligomer synthesized by using a polyoxyalkylene polyol and a polyisocyanate as a raw material, and is non-hardened. The oligomer (D) is a polyoxyalkylene polyol which is particularly preferable in terms of compatibility.

Even if the hydroxyl group-containing compound used as a raw material of the oligomer (A) or the oligomer (C) is different from the hydroxyl group-containing compound used as the non-curable oligomer (D), the hydroxyl group-containing compounds are still molecules of each other. The chain has a common repetitive unit or the like having a partially common structure, and the degree of polarity is preferably the same. The oligomer (A), the oligomer (C), and the non-curable oligomer (D) have a partially identical molecular structure, and the compatibility of the non-hardenable oligomer (D) in the composition is more improve.

As a method of adjusting the polarity of the hydroxyl group-containing compound, for example, a method of introducing a polar group and a method of preparing a hydroxyl group-containing compound having an oxygen-extended alkyl group having an oxygen-extended propyl group and an oxygen-extended ethyl group can be mentioned. As long as the polar group is introduced, the polarity of the hydroxyl group-containing compound increases. Further, as long as a hydroxyl group-containing compound having an oxygen-extended alkyl group having an oxygen-extended propyl group and an oxygen-extended ethyl group is formed, the polarity of the hydroxyl group-containing compound is increased. These methods can also be used in combination.

When a hydroxyl group-containing compound used as a raw material of the oligomer (A) or the oligomer (C) and a hydroxyl group-containing compound used as the non-curable oligomer (D) are different, a preferred combination thereof may be exemplified by the following combination .

The oligomer (A) or the oligomer (C) is a urethane acrylate synthesized by using a polyoxyl-propyl polyol and a polyisocyanate in which a part of the oxygen-extension propyl group has been substituted with an oxygen-extended ethyl group. Oligomer, non-hardening oligomer (D) A polyoxyalkylidene polyol which does not have an oxygen-extended ethyl group and which has a molecular weight per one hydroxyl group smaller than that of the polyol used as the oligomer (A) is a preferred combination.

The combination of the oligomer (A), the oligomer (C) and the non-curable oligomer (D) contained in the first composition is the following oligomer (A11), oligomer (C11) and The combination of the following non-curable oligomers (D1) is optimal.

Oligomer (A11): a polyoxyalkylene glycol having an oxygen-extended propyl group and an oxygen-extended ethyl group, and reacting with a polyisocyanate to obtain a prepolymer having an isocyanate group at the terminal, and then reacting the monomer with the above-mentioned monomer (a1) A polyurethane acrylate oligomer obtained by carrying out a reaction.

Oligomer (C11): a polyoxyalkylene alkyl alcohol having an oxygen-extended propyl group and an oxygen-extended ethyl group is reacted with a polyisocyanate to obtain a prepolymer having an isocyanate group at one end, and is then subjected to the foregoing A polyurethane monoacrylate oligomer obtained by reacting the body (c1).

Non-hardening oligomer (D1): a polyoxyalkylene glycol having an oxygen-extended propyl group and an oxygen-extended ethyl group, which is the same as the raw material of the oligomer (A11).

Further, the combination of the oligomer (A) and the non-curable oligomer (D) contained in the first composition is preferably the oligomer (A11), the oligomer (C11), and the following A combination of non-hardening oligomers (D2).

Non-hardening oligomer (D2): a polyoxypropylene glycol having an oxygen-extended propyl group and a polyoxypropylene glycol having a molecular weight smaller than that of the oligomer (A11).

When the non-curable oligomer (D) is used, the content of the non-curable oligomer (D) in the first composition (100% by mass) is preferably from 1 to 35% by mass. non- When the content of the curable oligomer (D) is at least the lower limit value, it is difficult to leave voids between the adhesive layer and the face material. When the content of the non-curable oligomer (D) is at most the upper limit value and the layer portion is sufficiently cured, the protective film can be easily peeled off from the cured adhesive layer.

When the non-curable oligomer (D) is used, the oligomer ((100% by mass)) of the oligomer (C) and the non-curable oligomer (D) in the first composition (oligomer) The ratio of C) is preferably 50% by mass or more, and more preferably 70% by mass or more. When the ratio of the oligomer (C) is at least the above lower limit value, it is easy to suppress generation or residual voids between the layered portion and the face material. The upper limit of the ratio of the aforementioned oligomer (C) is 100% by mass.

Further, the chain transfer agent also contributes to shortening the time until the gap between the face material and the adhesive layer is formed until it disappears.

The first composition does not contain a chain transfer agent, and contains the monomer (B1) and the monomer (B2), and the mass ratio of the monomer (B2) to the monomer (B1) is 0.6 to 2.5, the first composition ( The content of the non-curable oligomer (D) in 100% by mass is preferably from 30 to 70% by mass, more preferably from 40 to 70% by mass.

The first composition contains 1 part by mass or less of a chain transfer agent with respect to 100 parts by mass of the total of the oligomer (A), the monomer (B), and the oligomer (C), and the monomer (B2) content is less than a single In the case of the body (B1), the content of the non-curable oligomer (D) in the first composition (100% by mass) is preferably 40 to 70% by mass, more preferably 50 to 70% by mass.

The first composition contains the monomer (B1) and the monomer (B2), and the mass ratio of the monomer (B2) to the monomer (B1) is 1 to 3, and is relative to the oligomer (A) and the monomer ( B) and the non-hardening oligomer (D) content in the first composition (100% by mass) when 100 parts by mass of the total amount of the oligomer (C) is contained in an amount of 1 part by mass or less based on the chain transfer agent It is preferably 5 to 55 mass%, more preferably 10 to 50 mass%, and particularly preferably 35 to 50 mass%.

Further, when the first composition contains the monomer (B2) or the chain transfer agent, the curing rate tends to be slow, so that the monomer (B2) and the chain transfer agent are preferably used in a small amount.

In the present invention, the first composition is 6 to 80% by mass based on the total of the oligomer (A), the monomer (B) and the oligomer (C) (100% by mass), and the oligomer (A). The monomer (B) is 3 to 70% by mass and the oligomer (C) is preferably 10 to 70% by mass, the oligomer (A) is 6 to 60% by mass, and the monomer (B) is 3 to 55%. The mass% and the oligomer (C) are preferably from 30 to 70% by mass.

In the present invention, when the first composition contains the non-curable oligomer (D), it is relative to the oligomer (A), the monomer (B), the oligomer (C), and the non-curable oligomer (D). In total (100% by mass), the oligomer (A) is 6 to 80% by mass, the monomer (B) is 3 to 70% by mass, and the oligomer (C) is 5 to 69% by mass and non-hardening property. The oligomer (D) is preferably 1 to 35% by mass, the oligomer (A) is 6 to 60% by mass, the monomer (B) is 3 to 55% by mass, and the oligomer (C) is 15 to 69. The mass% and the non-curable oligomer (D) are preferably from 1 to 35% by mass.

The viscosity of the first composition is preferably from 0.05 to 50 Pa‧s, preferably from 1 to 20 Pa‧s. When the viscosity of the first composition is 0.05 Pa ‧ s or more, when the layered portion is obtained by the production method described later, the coating shape of the first component to be the layered portion can be maintained until the layer is laminated, and after lamination When returning to an atmospheric pressure environment, even if a void is generated, it is easy to become an independent void, and the void volume can be reduced by the pressure in the void (maintaining the pressure reduction) and the differential pressure applied to the pressure of the adhesive layer (atmospheric pressure), thereby making the void Easy to disappear, so it is available A hardened film without bubble residue. When the viscosity of the first composition is 50 Pa·s or less, it is difficult to leave a void between the layered portion and the face material.

The viscosity of the first composition was measured at 25 ° C using an E-type viscometer.

(Photopolymerization initiator (E1))

The photopolymerization initiator (E1) may, for example, be an acetophenone system, a ketal system, a benzoin or a benzoin ether system, a phosphine oxide system, a diphenyl ketone system or a 9-oxosulfuric acid. A photopolymerization initiator such as a lanthanide or a lanthanide. As a photopolymerization initiator (E1), a phosphine oxide system, 9-oxosulfur A photopolymerization initiator is preferred, and a phosphine oxide is preferred from the viewpoint of suppressing coloration after photopolymerization.

The photopolymerization initiator (E1) content in the photocurable first composition is 0.01 to 10 parts by mass based on 100 parts by mass of the total of the oligomer (A), the monomer (B) and the oligomer (C). Preferably, it is preferably 0.1 to 5 parts by mass.

(additive)

Examples of the additive include a polymerization inhibitor, a photocuring accelerator, a chain transfer agent, a light stabilizer (ultraviolet absorber, a radical scavenger, etc.), an antioxidant, a flame retardant, and an adhesion enhancer (a decane coupling agent, etc.). ), pigments, dyes, etc. As the additive to be added to the first composition, a polymerization inhibitor or a light stabilizer is preferred. In particular, the storage stability of the first composition can be improved by the polymerization inhibitor having a smaller amount than the polymerization initiator, and the molecular weight of the layered portion after curing can be adjusted.

Examples of the polymerization inhibitor include hydroquinone (2,5-di-tertiary butylhydroquinone, etc.), catechol (for tertiary butylcatechol), lanthanide, and thiophene. A polymerization inhibitor such as a hydroxytoluene system.

As the light stabilizer, there may be mentioned an ultraviolet absorber (benzotriazole system, two A phenyl ketone type, a salicylate type, etc.), a radical scavenger (hindered amine type), etc.

Examples of the antioxidant include phosphorus-based and sulfur-based compounds.

The content of the additive in the first composition is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the total of the oligomer (A), the monomer (B) and the oligomer (C). .

The storage shear modulus of the layered portion after the first composition is hardened at 35 ° C is preferably 0.5 to 100 kPa. The lower limit of the storage shear modulus is preferably 0.8 kPa. The upper limit of the storage shear modulus is preferably 80 kPa, more preferably 70 kPa. When the storage shear elastic modulus is in the above range and is bonded to the bonded surface material, the gap formed at the interface between the layered portion and the beak portion is easily lost at the interface between the bonded surface material and the adhesive layer. . Moreover, the bonded surface material can be favorably fixed in the laminated body obtained by bonding the bonded surface material and the transparent surface material.

The storage shear elastic modulus of the layered portion at 35 ° C was measured using a rheometer (Anton Paar Co., Ltd., modular rheometer Physica MCR-301) to measure the rotating shaft and the translucent fixing plate. The gap is the same as the thickness of the layered portion, and the first composition which is not hardened is disposed in the gap, and the storage shear elasticity of the hardening process is measured while applying heat or light required for hardening to the first composition which is not hardened. In the modulus, the measured value of the hardening condition at the time of forming the layer portion is the storage shear modulus of the layer portion.

The storage shear modulus can be adjusted by the amount of the oligomer (C) blended, and the larger the amount of the oligomer (C), the larger the storage shear modulus. Further, the storage shear modulus can also be adjusted by blending the non-curable oligomer (D).

Transparent surface material with adhesive layer≫

Fig. 1 is a cross-sectional view showing an example of a transparent face material with an adhesive layer of the present invention.

The transparent surface material 1 with an adhesive layer has a transparent surface material 10 (protective plate), a light-shielding printing part 12 formed in the peripheral part of the surface of the transparent surface material 10, and the surface of the transparent surface material 10 formed in the side of the light-shielding printing part 12. The adhesive layer 14 and a peelable protective film 16 (protective material) covering the surface of the adhesive layer 14.

The transparent surface material 1 to which the adhesive layer is attached can be bonded to the display panel after peeling off the protective film 16, and the display device can be manufactured.

In Fig. 1, the adhesive layer 14 is formed on one side of the transparent surface material 10, but the adhesive layer may be formed on both sides of the transparent surface material. At that time, the surface of any of the adhesive layers is covered with a peelable protective film.

<Transparent surface material>

The transparent surface material 10 is preferably a protective plate provided on the image display side of the display panel to protect the display panel.

The transparent surface material 10 is, for example, a glass plate or a transparent resin plate. As the transparent surface material 10, in terms of high transparency to the emitted light and the reflected light from the display panel, it is desirable that the glass plate is optimal in terms of light resistance, low birefringence, high planar precision, and surface damage resistance. And the high mechanical strength also seems to be the best glass plate. Further, the transparent face material 10 is preferably a glass plate in terms of sufficiently transmitting light for curing the photocurable resin composition.

As a material of the glass plate, a glass material such as soda lime glass can be mentioned. As the glass plate, a high light-transmissive glass (white plate glass) having a low iron content and a small blue color is preferable. As a glass plate, it is also possible to use reinforcement for safety. glass. Especially when using a thin glass plate, it is preferred to use a glass plate to which chemical strengthening has been applied.

The material of the transparent resin sheet may, for example, be a resin material (polycarbonate, polymethyl methacrylate or the like) having high transparency.

In order to improve the adhesion to the interface with the adhesive layer 14, the transparent face material 10 may also be subjected to a surface treatment. As a method of surface treatment, a method of treating the surface of the transparent surface material 10 with a decane coupling agent, and a method of forming a ruthenium oxide film by an oxidizing flame of a flame burner may be mentioned.

In order to improve the contrast of the display image, an anti-reflection layer may be provided on the surface of the transparent surface material 10 opposite to the side on which the adhesive layer 14 is formed. The method of providing the antireflection layer may be a method of directly forming an inorganic thin film on the surface of the transparent surface material 10, and a method of bonding a transparent resin film provided with an antireflection layer to the transparent surface material 10.

Further, depending on the purpose, a part or the whole of the transparent surface material 10 may be colored, or a part or the whole of the surface of the transparent surface material 10 may be ground into a glass shape to scatter light, or a part or the whole of the surface of the transparent surface material 10 may be used. The fine unevenness or the like is formed to refract or reflect the transmitted light. Further, a colored film, a light-scattering film, a light-refractive film, a light-reflecting film, or the like may be attached to a part or the entire surface of the transparent surface material 10.

The shape of the transparent facestock 10 is generally rectangular in the shape of the shape of the display device. A protective plate covering the entire surface of the display surface of the display panel and having a shape including a curved shape may be used depending on the shape of the display device.

The size of the transparent surface material 10 can be appropriately set in accordance with the shape of the display device.

The thickness of the transparent face material 10 is from the viewpoint of mechanical strength and transparency. If it is a glass plate, it is usually 0.5 to 25 mm. For applications such as television receivers and PC monitors used in indoors, it is preferably 1 to 6 mm from the viewpoint of weight reduction of the display device, and 3 to 20 mm for public display applications installed outdoors. When chemically strengthened glass is used, the thickness of the glass is preferably from 0.5 to 1.5 mm in terms of strength. In the case of a transparent resin sheet, the thickness of the transparent resin sheet is preferably 2 to 10 mm.

<Light-shielding printing section>

The light-shielding printing portion 12 is for concealing a wiring member or the like that is connected to the display panel so that a portion other than the image display region of the display panel, which will be described later, cannot be visually observed from the side of the transparent surface member 10. The light-shielding printing portion 12 may be formed on the side on which the adhesive layer 14 is to be formed or the side opposite thereto. In order to reduce the parallax between the light-shielding printing portion 12 and the image display region, it is preferable to form the light-shielding printing portion 12 on the surface on which the adhesive layer 14 is to be formed. When the transparent surface material 10 is a glass plate, it is preferable to use a ceramic printing containing a black pigment in the light-shielding printing part 12, and it is high in light-shielding property.

The wiring member or the like of the display panel cannot be visually observed from the side where the display panel is viewed, or when the other member such as the frame of the display device is concealed, or the transparent surface of the adherend and the adhesive layer other than the display panel When the material 1 is bonded, there is a case where the light-shielding printing portion 12 is not formed in the transparent surface material 10.

<adhesive layer>

The adhesive layer 14 has a layer portion 18 that extends along the surface of the transparent surface material 10, and a weir portion 20 that is joined to the periphery of the layer portion 18 and surrounds it.

The layer portion 18 is a portion composed of a cured product (transparent resin) formed by curing the first composition of the present invention.

The weir portion 20 is formed by applying a second composition described later and hardening it. A portion of the cured product (transparent resin).

[Layered part]

The layered portion 18 is preferably a cured product of a photocurable resin composition containing a photopolymerization initiator (E1) from the viewpoint of being hardenable at a low temperature and having a high curing rate.

The thickness of the layer portion 18 is preferably 0.03 to 2 mm, and more preferably 0.1 to 0.8 mm. When the thickness of the layered portion 18 is equal to or greater than the lower limit value, the layered portion 18 can effectively buffer the punching or the like due to the force from the side of the transparent surface material 10, thereby protecting the display panel or the like. Further, in the method of manufacturing a display device of the present invention, even if foreign matter not exceeding the thickness of the layer portion 18 is mixed between the display panel and the transparent surface material 1 to which the adhesive layer is applied, the thickness of the layer portion 18 is not greatly increased. Changes, and have little effect on light transmission performance. When the thickness of the layer portion 18 is equal to or less than the upper limit value, it is difficult to leave a void in the layer portion 18, and the overall thickness of the display device is not thicker than the desired thickness.

[堰部]

The second composition forming the weir portion 20 may be a photocurable resin composition or a thermosetting resin composition. The beak portion 20 is preferably a cured product of a photocurable resin composition containing a curable compound and a photopolymerization initiator (E2) from the viewpoint of being hardenable at a low temperature and having a high curing rate. Further, the second composition is not required to be cured at a high temperature as long as it is a photocurable resin composition, and therefore there is little risk of damage to the display panel due to high temperature.

Further, a second composition having the same composition as that of the first composition for forming the layer portion may be applied to the peripheral portion of the surface of the transparent surface material and semi-hardened to prepare the step (X4) described later or Unhardened 堰 before hardening in step (Y4) Shape.

The second composition may, for example, be a decyloxy resin (organic polysiloxane), an urethane oligomer or an urethane acrylate oligomer.

The viscosity of the second composition at 25 ° C is preferably 500 to 3000 Pa‧s, preferably 800 to 2500 Pa‧s, more preferably 1000 to 2000 Pa‧s. When the viscosity of the second composition is 500 Pa ‧ or more, the shape of the ridge portion before curing can be maintained for a long period of time, and the height of the ridge portion before curing can be sufficiently maintained. As long as the viscosity of the second composition is 3,000 Pa s, the ridge portion before curing can be formed by coating.

Further, the viscosity of the second composition forming the weir portion at the time of coating is less than 500 Pa s, and if the second composition is a photocurable resin composition, the light is irradiated after the application, and the light is irradiated. The viscosity of the second composition may be within the above desired range. From the viewpoint of coating easiness, the viscosity of the second composition at the time of coating is preferably 500 Pa ‧ or less, more preferably 200 Pa ‧ or less.

The viscosity of the second composition was measured at 25 ° C using an E-type viscometer.

Further, in order to maintain the distance between the transparent face material 10 and the display panel, spacer particles having a predetermined particle diameter may be blended in the second composition.

As the second composition, a composition containing the oligomer (G), the monomer (H), and the photopolymerization initiator (E2) is preferred.

The oligomer (G) is an oligomer having a curable functional group and a number average molecular weight of 30,000 to 100,000.

Monomer (H) has a hardening functional group and a molecular weight of 125 to 600 monomer.

Examples of the curable functional group of the oligomer (G) and the monomer (H) include an acryloxy group and a methacryloxy group. As the curable functional group of the oligomer (G) and the monomer (H), propylene oxy or methacrylic acid is used from the viewpoint of a fast curing rate and a cleavage portion having high transparency. The oxy group is preferred. Further, from the viewpoint of obtaining a layered portion in which the difference in reactivity between the oligomer (G) and the hardening functional group of the monomer (H) is reduced and homogenized, the oligomer (G) has a curable functional group. It is preferably an acryloxy group and the curable functional group of the monomer (H) is preferably a methacryloxy group.

The oligomer (G) has a number average molecular weight of 30,000 to 100,000, preferably 40,000 to 80,000, and preferably 50,000 to 65,000. When the number average molecular weight of the oligomer (G) is within the above range, the viscosity of the second composition is easily adjusted to the above range.

The molecular weight of the monomer (H) is from 125 to 600, preferably from 140 to 400, and preferably from 150 to 350. When the molecular weight of the monomer (H) is at least 125, the volatilization of the monomer (H) can be suppressed when a laminate such as a display device is produced. When the molecular weight of the monomer (H) is 600 or less, the solubility of the monomer (H) to the high molecular weight oligomer (G) can be improved, and the viscosity adjustment as the second composition can be suitably performed.

The average number of the curable functional groups of the oligomer (G) is preferably from 1.8 to 4 from the viewpoint of the curability of the first composition and the mechanical properties of the layer portion.

As the oligomer (G), there may be mentioned an amine urethane oligomer having an urethane bond, a poly(meth) acrylate of a polyoxyalkylene polyol, and a poly(polyol). Base) acrylate and the like.

An amine synthesized by using a polyol and a polyisocyanate as a raw material from the viewpoint of greatly improving the mechanical properties of the cured resin and the adhesion to the surface material by molecular design of the urethane chain The ethyl formate oligomer is preferred, and the oligomer (G1) described later is preferred. The polyhydric alcohol is preferably a polyoxyalkylene polyol.

(oligomer (G1))

The oligomer (G1) having a number average molecular weight of from 30,000 to 100,000 is highly viscous, so that it is difficult to synthesize in a general method, and it is difficult to mix with the monomer (H) even if the synthesis is successful.

Therefore, it is preferred to synthesize the oligomer (G1) by using a synthesis method of the monomer (H) (the following monomers (H1) and (H2)), and then use the obtained product as a second composition. Alternatively, the obtained product is further diluted with a monomer (H) (the following monomer (H1), monomer (H3), etc.) to be used as a second lipid composition.

Monomer (H1): a monomer having a hardening functional group in the monomer (H) and having no reaction with an isocyanate group.

Monomer (H2): a monomer having a hardenable functional group and having a group reactive with an isocyanate group in the monomer (H).

Monomer (H3): a monomer having a curable functional group and having a hydroxyl group in the monomer (H).

Method for synthesizing oligomer (G1): a method in which a polyol is reacted with a polyisocyanate in the presence of a monomer (H1) as a diluent to obtain a prepolymer having an isocyanate group, and then a monomer (H2) The reaction of the isocyanate group of the prepolymer.

As the polyhydric alcohol or polyisocyanate, a known compound can be mentioned, for example. In the pamphlet of International Publication No. 2009/016943, the polyol (i), the diisocyanate (ii) and the like described in the raw material of the urethane-based oligomer (a) are used.

As a specific example of the polyol, the same as the polyol exemplified in the first composition can be used. The type of the polyol may be the same as or different from the first composition, and the same is preferred. Further, it is more preferable to use a polyoxyalkylene polyol having an oxygen-extended alkyl group having an oxygen-extended propyl group and an oxygen-extended ethyl group to improve the compatibility of the second composition with other components.

The polyhydric alcohol may be one type or two or more types.

As the polyisocyanate, the same as the polyisocyanate exemplified in the first composition can be used. The polyisocyanate may be the same as or different from the first composition, and the same is preferred.

The polyisocyanate may be one type or two or more types.

The monomer (H1) may, for example, be an alkyl (meth)acrylate having an alkyl group having 8 to 22 carbon atoms (n-dodecyl (meth)acrylate or n-octadecyl (meth)acrylate, ( (meth)acrylic acid ester, etc.), and (meth)acrylic acid ester ((meth)acrylic acid ester) having an alicyclic hydrocarbon group Ester, adamantyl (meth)acrylate, etc.).

The monomer (H2) may, for example, be a monomer having an active hydrogen (hydroxyl group, an amine group or the like) and a curable group. Specific examples of the monomer (H2) include a hydroxyalkyl (meth)acrylate having a hydroxyalkyl group having 2 to 6 carbon atoms (2-hydroxyethyl (meth)acrylate, (meth)acrylic acid). 2-hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.). Among them, as the monomer (H2), a hydroxyalkyl acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms is preferred.

The monomer (H) may also be included in the synthesis method of the oligomer (G1). Monomer (H1) used as a diluent. Further, the monomer (H) may also contain an unreacted monomer (H2) used in the synthesis method of the oligomer (G1).

Moreover, it is preferable that the monomer (H) contains a monomer (H3) from the viewpoints of the adhesion between the face material and the weir portion and the solubility of various additives described later.

As the monomer (H3), a hydroxy methacrylate having a hydroxyl group of 1 to 2 and a carbon number of 3 to 8 (2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, A) Preferably, 4-hydroxybutyl acrylate, 6-hydroxyhexyl methacrylate or the like is preferred, and 2-hydroxybutyl methacrylate is preferred.

The ratio of the monomer (H) in the second composition is preferably 15 to 50% by mass, and 20 to 45% by mass based on the total of the oligomer (G) and the monomer (H) (100% by mass). Preferably, it is preferably from 25 to 40% by mass. When the ratio of the monomer (H) is 15% by mass or more, the hardenability of the second composition and the adhesion between the face material and the beak portion are preferable. When the ratio of the monomer (H) is 50% by mass or less, the viscosity of the second composition is easily adjusted to 500 Pa‧s or more.

However, in the synthesis of the oligomer (G1), the monomer (H2) which has reacted with the isocyanate group of the prepolymer is partially present as one of the oligomers (G), and thus is not contained in the second composition. In the monomer (H) content. On the other hand, in the synthesis of the oligomer (G1), the monomer (H1) used as a diluent and the monomer (H) added after the synthesis of the oligomer (G1) are contained in the second composition. In the ratio of monomer (H).

(Photopolymerization initiator (E2))

The photopolymerization initiator (E2) contained in the photocurable second composition may, for example, be an acetophenone system, a ketal system, a benzoin or a benzoin ether system, a phosphine oxide system or a diphenyl group. Ketone system, 9-oxosulfur A photopolymerization initiator such as a lanthanide or a lanthanide. Among them, a photopolymerization initiator (E2) is preferably an acetophenone-based, ketal-based or benzoin-ether photopolymerization initiator. When hardening is performed by visible light having a short wavelength, a phosphine oxide photopolymerization initiator is preferred from the viewpoint of absorption wavelength region. By using two or more kinds of photopolymerization initiators (E2) having different absorption wavelength regions in combination, the hardening time can be further accelerated, and the surface hardenability in the beak portion can be improved.

The photopolymerization initiator (E2) content in the photocurable second composition is preferably 0.01 to 10 parts by mass, and 0.1 to 5 parts by mass based on 100 parts by mass of the total of the oligomer (G) and the monomer (H). The mass portion is preferred.

(additive)

The additive added to the second composition may be the same as those enumerated in the first composition. As the additive to be added to the second composition, a polymerization inhibitor or a light stabilizer is preferred. In particular, by containing a polymerization inhibitor having a smaller amount than the polymerization initiator, the storage stability of the second composition can be improved, and the molecular weight of the beak portion after hardening can be adjusted.

The total amount of the additives is preferably 10 parts by mass or less, and preferably 5 parts by mass or less, based on 100 parts by mass of the total of the oligomer (G) and the monomer (H).

Generally, the outer area of the image display area of the display panel is narrow, so it is preferable to narrow the width of the beak portion 20. The width of the beak 20 is preferably 0.5 to 2 mm, and preferably 0.8 to 1.6 mm.

The shear modulus of the beak 20 at 35 ° C is preferably greater than the shear modulus of the layer 18 at 35 ° C. When the shear modulus of the beak portion 20 is larger than the shear elastic modulus of the layer portion 18, when the display panel and the transparent surface material 1 with the adhesive layer are bonded, even on the periphery of the adhesive layer 14 on the display panel and There is a void at the interface of the adhesive layer 14, and the void is also difficult to open to the outside, and it is easy to become an independent void. Therefore, when the display panel is bonded to the transparent surface material 1 with the adhesive layer in a reduced-pressure atmosphere, and then returned to the atmospheric pressure environment, the pressure in the void (maintaining the reduced pressure) is applied to the adhesive layer. The differential pressure of the pressure of 14 (atmospheric pressure) reduces the void volume and makes the void easily disappear.

The difference between the thickness of the beak portion 20 and the thickness of the layer portion 18 is preferably 0.05 mm or less from the viewpoint of suppressing the void generated by the step of the beak portion 20 and the layer portion 18, and is preferably 0.03 mm or less. good.

The difference between the thickness of the beak 20 and the thickness of the layer portion 18 is measured by a laser displacement gauge, and the total thickness of the transparent face material 10 and the layered portion 18 or the beak portion 20 formed thereon is measured and Poor to calculate. Further, the thickness of the layer portion 18 is the thickness of the peripheral portion of the layer portion 18 that is in contact with the weir portion 20.

When at least a portion of the region where the beak portion 20 and the layer portion 18 are close to each other, the thickness of the beak portion 20 is thicker than the thickness of the layer portion 18, the thickness of the thinnest portion of the layer portion 18 is relative to the beak portion 20 The ratio of the thickness is preferably 1/2 or more and preferably 99/100 or less. As long as the aforementioned ratio is within the above range, the voids 110 are not opened to the outside, and are easily formed as the independent voids 110.

[protective film]

The protective film 16 is required not to be firmly adhered to the adhesive layer 14, and to be attached to the support face material in a manufacturing method to be described later. Therefore, the protective film 16 is preferably a self-adhesive protective film in which one surface of a base film having low adhesion such as polyethylene, polypropylene, or a fluorine-based resin is an adhesive surface.

The adhesive film of the protective film 16 is peeled under the peeling speed of the protective film 16 of the 50 mm width with respect to the acrylic sheet by a peeling speed of 300 mm/min. The adhesive force should be 0.01~0.1N, preferably 0.02~0.06N. The adhesive force can be attached to the support surface material as long as it is at least the lower limit value. When the adhesive force is at most the upper limit value, the protective film 16 is easily peeled off from the support surface material.

The thickness of the protective film 16 varies depending on the resin to be used. When a soft film such as polyethylene or polypropylene is used, it is preferably 0.04 to 0.2 mm, and preferably 0.06 to 0.1 mm. When the thickness of the protective film 16 is at least the lower limit value, deformation of the protective film 16 can be suppressed when the protective film 16 is peeled off from the adhesive layer 14. When the thickness of the protective film 16 is equal to or less than the upper limit value, the protective film 16 is easily deflected at the time of peeling, and the protective film 16 can be easily peeled off from the adhesive layer 14.

Further, since the back surface layer is provided on the back surface of the protective film 16 opposite to the adhesive surface, it is easier to peel off from the adhesive layer 14. As the back layer, a film having a low adhesion such as polyethylene, polypropylene or a fluorine-based resin is preferably used. In order to more easily peel off the protective film 16, a release agent such as xenon oxide may be applied to the protective film 16 in a range that does not adversely affect the adhesive layer 14.

[Support surface material]

As the supporting face material, it is preferable to use a face material having a smooth surface and being rigid. For example, glass, a transparent resin plate, etc. are preferable, and glass is especially preferable from the viewpoint that the substance itself does not absorb UV light. The material of the glass can be any of tempered glass and non-reinforced glass.

[other forms]

However, the transparent surface material 1 of the adhesive layer of the illustrated example is an example of a protective plate of the display device, but the transparent surface material of the adhesive layer of the present invention is not limited by the illustrated example, as long as it is at least a face material. A surface may be formed with a specific adhesive layer.

Further, the transparent surface material with an adhesive layer of the present invention may be provided with a polarizing mechanism (film-shaped absorbing polarizer, wire grid polarizer, etc.) between the surface material (protective plate) and the specific adhesive layer, and light modulation. A mechanism (a retardation film such as a 1⁄4 wavelength plate, a phase difference film whose pattern is processed into a stripe shape, etc.).

制造How to make transparent surface material with adhesive layer≫

The method for producing the transparent surface material with an adhesive layer of the present invention may, for example, be a method having the following steps (X1) to (X5).

In the step (X1), a liquid second composition is applied to the peripheral portion of the surface of the face material to form an unhardened weir portion.

In the step (X2), the liquid first composition is supplied to a region surrounded by the unhardened weir portion of the surface of the face material.

Step (X3), in a vacuum gas atmosphere of 100 Pa or less, the support surface material to which the protective film has been attached is superposed on the first composition so that the protective film is in contact with the first composition, thereby obtaining no The hardened layered portion is formed of a transparent face material, a protective film, and a precursor layer sealed by an unhardened weir, and the unhardened layered portion is composed of the first composition.

In the step (X4), the unhardened layered portion and the uncured beak portion are hardened to form an adhesive layer having a layered portion and a beak portion in a state where the precursor laminate is placed under a pressure of 50 kPa or more. .

In step (X5), the support face material is peeled off from the protective film.

The method for producing a transparent surface material with an adhesive layer according to the present invention is such that the first composition is sealed between the surface material and the protective film attached to the support surface material under a reduced pressure gas atmosphere, and is equal in an atmospheric pressure environment. A method of hardening a sealed first composition to form a layered portion in a pressurized gas atmosphere. In reduction The method of enclosing the first composition is not a method of injecting the first composition into a narrow and wide space between the face material and the protective film attached to the supporting face material, but is applied to the transparent surface. The first composition is supplied to the first surface of the material, and then the protective film adhered to the supporting surface material is superposed, and the first composition is sealed between the surface material and the protective film adhered to the supporting surface material. .

An example of a method for producing a transparent laminate in which a curable resin composition is sealed under reduced pressure and a curable resin composition is cured under an atmospheric pressure environment is known. For example, International Publication No. 2008/81838 and International Publication No. 2009/16943 disclose a method for producing a transparent laminate and a curable resin composition used in the method. In the production of the transparent surface material with an adhesive layer of the present invention, in addition to the use of the first composition of the present invention, the production methods described in these documents may be employed.

Since the transparent surface material of the adhesive layer of the present invention contains the oligomer (C) in the first composition, the fluidity of the layered portion is high, and voids remain in the layered portion sealed under reduced pressure at the time of production. The void can still disappear in a short period of time by the pressure in the gap and the pressure applied to the adhesive layer when the pressure is restored. Moreover, since the transparent surface material of the adhesive layer of the present invention contains the oligomer (C), the layered portion has low elasticity, and the stress applied to the bonded display panel is small, and display unevenness can be suppressed. The transparent face material with the adhesive layer as described above is suitable as a protective plate for the display device.

≪层层≫

The laminated body of the present invention has a pair of face materials and an adhesive layer, and the adhesive layer is formed between the face materials to be in contact with the opposing faces, and has a layered portion and a beak portion; and the layer The first component of the present invention Made up of hardened matter.

The laminate of the present invention is useful for laminated glass (windproof glass, safety glass, anti-theft glass, etc.), display, and solar cells.

The laminate of the present invention is particularly useful for a display device having a one side material as a display panel and the other side material being a transparent surface material.

<Action effect>

In the laminate of the present invention, by using the first composition containing the oligomer (C) having an average number of curable functional groups of 0.5 to 1, the same effect as that of the non-hardening oligomer can be obtained, and Even after a predetermined period of time after the formation of the adhesive layer, the occurrence or residual voids at the interface between the adhesive layer and the bonded surface material can be sufficiently suppressed.

Manufacturing method of stratified layer

The method for producing the laminated body of the present invention includes a method (x) of using a transparent surface material with an adhesive layer described later, and a method (y) of using a transparent surface material with an adhesive layer.

The method (x) is a method in which the transparent surface material of the adhesive layer and the other surface material (the bonded surface material) of the non-adhesive layer are bonded to each other by the adhesive layer in a reduced pressure gas atmosphere of 1 kPa or less. The method of overlapping fits.

Further, the method (y) has the following steps (Y1) to (Y4).

In the step (Y1), a liquid second composition for forming a weir portion is applied to the peripheral portion of the surface of the one surface to form an unhardened weir portion.

In the step (Y2), the liquid first composition is supplied to a region surrounded by the uncured weir portion on the surface of the one side material.

Step (Y3), the other side is under a reduced pressure gas atmosphere of 1 kPa or less The material is superposed on the first composition, and the precursor layer which is sealed by the one side material, the other surface material and the unhardened weir portion is obtained from the unhardened layer portion, and the unhardened layer portion is composed of the first composition Composition.

In the step (Y4), the unhardened layered portion and the uncured beak portion are hardened to form an adhesive layer having a layered portion and a beak portion in a state where the precursor laminate is placed under a pressure of 50 kPa or more. .

Example

Hereinafter, the present invention will be described in detail by way of examples, but the invention should not be construed as limited.

[surface material]

In the peripheral portion of one surface of the soda-lime glass having a length of 100 mm, a width of 100 mm, and a thickness of 1.3 mm, the light-shielding portion is formed by ceramic printing containing a black pigment so that the light-transmitting portion is in a region of 68 mm in length and 68 mm in width. And make the face material -i.

[Support surface material]

A protective film (manufactured by MC-TOHCELLO Co., Ltd., Puretect VLH-9) having a length of 130 mm, a width of 130 mm, and a thickness of 0.75 mm was attached to the surface of the protective film by a rubber roller and attached to the glass by a length of 100 mm and a width of 100 mm. A transparent plate made of 3 mm thick soda lime glass is used to produce a support surface material -ii to which a protective film is attached.

[fitted surface material]

As a bonded surface material, it is a laminated surface material which is attached to a polarizing plate (manufactured by Polatechno Co., Ltd., KN-18240T) which is adhered to one of a soda lime glass having a length of 100 mm, a width of 100 mm, and a thickness of 1.7 mm. -iii, to Replace the LCD panel.

[Oligomer (A)]

Oligomer (A-1): a bifunctional polypropylene polyol whose molecular end is modified with ethylene oxide (a number average molecular weight calculated from a hydroxyl value (28 mgKOH/g): 4000), and 3-isocyanide The acid methyl-3,5,5-trimethylcyclohexyl diisocyanate was mixed at a molar ratio of 4:5 and reacted at 70 ° C in the presence of a tin catalyst to obtain an isocyanate terminal prepolymer. To the obtained isocyanate terminal prepolymer, 2-hydroxyethyl acrylate was added to make the same equivalent amount as the isocyanate group of the prepolymer, and reacted at 70 ° C to obtain an oligomer (A-1) (amino acid formic acid B) Ester acrylate oligomer). The oligomer (A-1) had two hardening functional groups of 2, a number average molecular weight of about 24,000, and a viscosity at 25 ° C of about 830 Pa‧s.

[Oligomer (C)]

Oligomer (C-1): a monofunctional polypropylene polyol (number average molecular weight calculated from a hydroxyl value (16.8 mg KOH/g): 3340), and isophorone diisocyanate (IPDI) in a molar ratio of 1 : 0.975 was mixed and reacted at 70 ° C in the presence of a tin catalyst to obtain an isocyanate terminal prepolymer. To the obtained isocyanate terminal prepolymer, 2-hydroxyethyl acrylate was added in the same equivalent amount as the isocyanate group of the prepolymer, and the mixture was reacted at 70 ° C to obtain an oligomer (C-1).

The average number of the curable functional groups of the oligomer (C-1) was 0.95, the number average molecular weight was about 3,500, and the viscosity at 25 ° C was about 880 mPa ‧ s. Oligomer (C-2): a monofunctional polypropylene polyol (a number average molecular weight calculated from a hydroxyl value (11.0 mgKOH/g): 5100), and 2-methylpropenyloxyethyl isocyanate The ear is mixed at 1:0.95 and in the presence of tin catalyst at 70 ° C The reaction was carried out to obtain an oligomer (C-2).

The average number of the curable functional groups of the oligomer (C-2) was 0.95, the number average molecular weight was about 5,100, and the viscosity at 25 ° C was about 1700 mPa ‧ s.

[non-hardening oligomer (D)]

Non-hardening oligomer (D-1): a 2-functional polypropylene polyol modified with ethylene oxide at the molecular end of the same as that used in the synthesis of the aforementioned oligomer (A-1) (by hydroxyl value ( The number average molecular weight calculated by 28 mg KOH/g): 4000).

[Resin composition for layer formation]

40 parts by mass of the oligomer (A-1), 30 parts by mass of 2-hydroxybutyl methacrylate (manufactured by Kyoei Chemical Co., Ltd., LIGHTESTER HOB) as a monomer (B1), and as a monomer (B2) 30 parts by mass of n-dodecyl methacrylate was uniformly mixed. Then, 0.3 parts by mass of the product name "IRGACURE 819" (photopolymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 2,5-di-tertiary butylhydroquinone (polymerization inhibition) were uniformly dissolved in 100 parts by mass of the mixture. 0.04 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd., product name "TINUVIN 109" (manufactured by Ciba Specialty Chemicals Co., Ltd., UV absorber) 0.3 parts by mass, and n-dodecyl mercaptan (chain transfer agent, manufactured by Kao Corporation, THIOKALCOL20) 0.3 parts by mass, and the matrix composition (P-1) was obtained.

70 parts by mass of the matrix composition (P-1) and 30 parts by mass of the non-curable oligomer (D-1) were uniformly dissolved, placed in a container, and placed in a decompression device in an open state, and the inside of the decompression device was placed. The mixture was depressurized to about 20 Pa for 10 minutes to carry out a defoaming treatment to obtain a composition-1.

Further, 70 parts by mass of the matrix composition (P-1), and oligomer (C-1) and oligo The mass of the polymer (C-2) was uniformly dissolved in 30 parts by mass of the 1:1 kneaded product, placed in a container and placed in a decompression device in an open state, and the pressure in the decompression device was reduced to about 20 Pa and kept at 10 Minutes were taken for defoaming treatment to obtain Composition-2.

The composition-1 and the composition-2 were uniformly mixed at a mixing ratio (unit: mass%) shown in Table 1, and the first composition-1 to the first composition-4 for forming a layer portion were obtained.

[Resin composition for forming a beak]

A bifunctional polypropylene polyol having a molecular end modified by ethylene oxide (a number average molecular weight calculated from a hydroxyl value (28 mg KOH/g): 4000), and a hexamethylene diisocyanate at a molar ratio of 6:7 Mix and add 30% by mass The acrylate (IBXA, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was reacted at 70 ° C in the presence of a tin catalyst to obtain an isocyanate terminal prepolymer. To the obtained isocyanate terminal prepolymer, 2-hydroxyethyl acrylate was added in the same equivalent amount as the isocyanate group of the prepolymer, and reacted at 70 ° C to obtain a 30% by mass difference. A urethane acrylate oligomer (hereinafter referred to as "oligomer (G1-1)") diluted with a acrylate (monomer (H)). The average number of the curable functional groups of the oligomer (G1-1) was 2, the number average molecular weight was 55,000, and the viscosity at 60 ° C was 580 Pa‧s.

90 parts by mass of the oligomer (G1-1) and 10 parts by mass of 2-hydroxybutyl methacrylate (LIGHTESTER HOB, manufactured by Kyoei Chemical Co., Ltd.) were uniformly mixed to obtain a mixture. 100 parts by mass of this mixture, 1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, Ciba Specialty Chemicals, IRGACURE 184) 0.9 parts by mass, bis(2,4,6-trimethylbenzene) Methionyl)-phenylphosphine oxide (photopolymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE 819) 0.1 parts by mass, 2,5-di-tertiary butylhydroquinone (polymerization inhibitor, Tokyo Chemical Industry Co., Ltd.) 0.04 parts by mass and 0.3 parts by mass of a UV absorber (manufactured by Ciba Specialty Chemicals Co., Ltd., TINUVIN 109) were uniformly mixed. The mixture is placed in a container and placed in a decompression device in an open state, and the pressure in the decompression device is reduced to about 20 Pa for 10 minutes to perform a defoaming treatment, thereby obtaining a second portion for forming a beak. Composition-1.

[example 1] (Step (X1))

The second composition-1 was coated with a spreader to a width of about 1 mm and a coating thickness of about 0.6 mm over the entire circumference of the position covering the inner edge of the light-shielding portion of the face material-i, and formed into a shape. unit.

Next, the ultraviolet rays from the chemical lamp (FL15BL, peak wavelength: 365 nm, irradiation intensity: 2 mW/cm ² ) and visible light of 450 nm or less were uniformly irradiated to the enamel portion formed on the face material -i for 30 seconds. bell. Thereby the ridge is thickened.

(Step (X2))

The first composition-1 was supplied to a plurality of places at a total mass of 2.5 g using a spreader in the inner region of the weir portion of the face material-i.

During the supply of the first composition-1, there is no breakage such as collapse and the shape of the beak is maintained.

(Step (X3))

The facestock-i is placed flat on the platform below the pressure reducing device of the lifting device provided with a pair of platforms in the upward facing manner of the first composition-1.

Using the electrostatic chuck, the support face material -ii to which the protective film has been attached is held under the upper platform of the lifting device in the pressure reducing device. The position of the protective film in the vertical direction is set at a distance of 10 mm from the face material -i.

The decompression device was sealed and evacuated until the pressure in the decompression device reached about 40 Pa. The upper and lower platforms are brought close to each other by a lifting device in the decompression device, and the face material-i and the supporting surface material-ii to which the protective film has been attached are crimped by the first composition-1 at a pressure of 2 kPa, and kept at 10 Seconds. The electrostatic chuck is de-energized so that the support surface material -ii is separated from the upper platform, and the pressure-reducing device is returned to the atmospheric pressure environment in about 15 seconds, thereby obtaining the layered portion through the surface material -i, the protective film and the beak-shaped seal. The precursor layer-1 is composed of the first composition-1.

In the precursor laminate-1, the shape of the weir portion is maintained substantially in the initial state.

(Step (X4))

The ray and the layered portion of the precursor layer-1 were uniformly irradiated with ultraviolet rays from a chemical lamp (made by Nippon Electric Co., Ltd., FL15BL, peak wavelength: 365 nm, irradiation intensity: 2 mW/cm ² ) from the support surface material -ii side. And visible light of 450 nm or less for 10 minutes, and the enamel portion and the layer portion are hardened, thereby forming an adhesive layer.

The irradiation intensity was measured using an illuminometer (manufactured by USHIO Electric Co., Ltd., UV intensity meter UNIMETER UIT-101). The layered portion after hardening has a thickness of 0.4 mm and is substantially uniform.

(Step (X5))

The support face material -ii of the precursor laminate-1 was peeled off from the protective film, whereby the transparent face material-1 to which the adhesive layer of the protective film was attached was obtained.

[Example 2~4]

In the same manner as in Example 1, except that the first composition type was changed as shown in Table 2, a transparent surface material-2 to which an adhesive layer was attached, and a transparent surface material-4 to which an adhesive layer was attached was obtained.

[Adhesive layer deformation evaluation] (1) Long-term storage accelerated test

The protective film was peeled off from the transparent surface material with the adhesive layer obtained in each example, and stored in a thermostat at 80 ° C for 5 days.

(2) Evaluation of deformation of the adhesive layer

The shape of the adhesive layer was evaluated using a digital microscope VHX-1000 manufactured by KEYENCE Corporation to measure the shape using the depth of focus. The measurement portion is a portion that spans the layered portion from the outer peripheral end portion of the crotch portion of the one side of the transparent surface material to which the adhesive layer is attached, and covers a distance of about 5 mm from the adhesive layer. In the measurement, a silver paste is thinly coated on the surface of the adhesive layer for the purpose of improving the sensitivity of the measurement. The measurement was carried out before and after the accelerated test of (1). The shape change is the amount of displacement of the beak and the layer before and after the accelerated test.

The deformation evaluation is to measure the edge of the resin and the layer resin in the inner part. The height is the center of the boundary, and the difference between the highest point of the resin in the width of 2 mm and the lowest point of the resin in the layer portion is calculated as the step (deformation amount).

[Evaluation of the gap between the steps of bonding with the bonded surface material]

The transparent surface material after the accelerated test of (1) evaluated by the aforementioned step and which has been peeled off from the protective film was subjected to vacuum degassing treatment. Thereafter, the transparent surface material with the adhesive layer was placed flat on the lower platform in the decompression device provided with the lifting device of the pair of platforms within 1 minute with the adhesive layer facing upward. The conditions of the vacuum degassing treatment were a gas ambient pressure of 100 Pa and a treatment time of 10 minutes.

The bonded face material -iii was held under the upper stage of the lifting device in the decompression device using an electrostatic chuck, and the distance between the bonded face material -iii and the transparent face material to which the adhesive layer was attached was set to 10 mm.

The pressure reducing device was sealed and evacuated until the pressure in the pressure reducing device reached about 30 Pa. The upper and lower platforms were brought close to each other by a lifting device in the decompression device, and the bonded surface material -iii and the transparent surface material with the adhesive layer were laminated and adhered for 10 seconds under a pressure of 2 kPa. The electrostatic chuck was de-energized and the bonded face material-iii was separated from the upper stage, and the inside of the decompression device was returned to atmospheric pressure in about 20 seconds to obtain a laminate.

As a result of observing the laminated body obtained by laminating the transparent surface material with the adhesive layer, most of the fine voids (bubbles) were found at the interface between the bonded surface material - iii and the adhesive layer of the transparent surface material to which the adhesive layer was attached. . The laminate was allowed to stand and evaluated for the disappearance of the void.

[Resin viscoelasticity evaluation (measurement of storage shear elastic modulus)]

The rheometer (manufactured by Anton Paar Co., Ltd., Physica MCR301) was used to hold the first composition on a soda-lime glass workbench and a measuring shaft (manufactured by Anton Paar Co., Ltd., D-PP20/AL/S07) of 0.4 mm. gap. In a nitrogen atmosphere, a black light (available from Nippon Electric Co., Ltd., FL15BL) provided at a lower portion of the table was applied at a temperature of 35 ° C, and a 1% dynamic was applied while irradiating the first composition with light of 2 mW/cm ^{2 for} 10 minutes. Shear strain was measured to determine the storage shear modulus of the layered portion of the adhesive layer.

The evaluation results in Examples 1 to 4 are shown in Table 2. Example 1 is a comparative example, and Examples 2 to 4 are examples. Further, (C)/((C)+(D)) in Table 2 represents the ratio of the oligomer (C) to the total of the oligomer (C) and the non-curable oligomer (D) ( quality%).

As shown in Table 2, the more the ratio of (C) / ((C) + (D)) in the first composition for forming the layered portion, the amount of deformation (step difference) generated on the surface of the adhesive layer after the accelerated test ) that is getting smaller. In the laminated body using the transparent surface material-1 having the adhesive layer containing the layered portion of the oligomer (C), the storage shear modulus is good, but it is attached to the bonded surface material. There is a residual void, after which the void remains until after 24 hours. On the other hand, a laminate of transparent face materials -2 to 4 having an adhesive layer containing a layered portion containing the oligomer (C) is used. In the case, it is confirmed that the void is destroyed or disappears with the passage of time after the accumulation.

1‧‧‧Transparent surface material with adhesive layer

10‧‧‧Transparent surface material

12‧‧‧Lighting Printing Department

14‧‧‧Adhesive layer

16‧‧‧Protective film

18‧‧‧Layered

20‧‧‧堰

Claims (11)

A curable resin composition for forming a layered portion in an adhesive layer, the adhesive layer being an adhesive layer for bonding a pair of face materials, and having a layered portion extending along a surface of the face material; the hardenability The resin composition contains the following oligomer (A), the following monomer (B), and the following oligomer (C): oligomer (A): a number average molecular weight of 1,000 to 100,000 and a hardening functional group The oligomer having an average of 1.8 to 4; the monomer (B): consisting of at least one monomer having a molecular weight of 125 to 600 and having a hardening functional group of 1 to 3, and comprising at least one monomer having a hydroxyl group Monomer (B1) monomer; oligomer (C): an oligomer having a number average molecular weight of 1,000 to 20,000 and an average number of hardening functional groups of 0.5 to 1; wherein the oligomer (A) is relative to the above The total amount of the monomer (B) and the oligomer (C) (100% by mass), the oligomer (A) is 6 to 80% by mass, and the monomer (B) is 3 to 70% by mass. The polymer (C) is 10 to 70% by mass. The curable resin composition of claim 1, which further contains a photopolymerization initiator (E1). The curable resin composition according to claim 1 or 2, further comprising the following non-curable oligomer (D): non-curable oligomer (D): not hardened with the aforementioned oligomer (A), The monomer (B) and the oligomer (C) are subjected to a hardening reaction, and have a hydroxyl group, and each hydroxyl group has an oligomer having a molecular weight of 400 to 8,000. The curable resin composition of claim 3, wherein the ratio of the oligomer (C) is the ratio of the oligomer (C) to the total of the non-curable oligomer (D) (100% by mass) 50~100% by mass. The curable resin composition of claim 1, wherein the curable functional group is an acryloxy group or a methacryloxy group. The curable resin composition of claim 1, wherein the oligomer (A) is obtained by reacting a polyol with a polyisocyanate to obtain a prepolymer having an isocyanate group at the end, and then the following monomer (a1) is used. a urethane acrylate oligomer obtained by reacting an isocyanate group of a prepolymer; and the aforementioned oligomer (C) is a prepolymer having an isocyanate group only at one end by reacting a unit alcohol with a polyisocyanate Thereafter, the oligomer obtained by reacting the following monomer (c1) with the isocyanate group of the prepolymer; monomer (a1): having a molecular weight of 125 to 600, having one or more acryloxy groups, and having One monomer which reacts with an isocyanate group; the monomer (c1): a monomer having a molecular weight of 125 to 600, having one or more acryloxy groups and having one reactive group with an isocyanate group. A transparent surface material with an adhesive layer, comprising a transparent surface material and an adhesive layer disposed on a surface of the transparent surface material; the adhesive layer has a layered portion extending along a surface of the transparent surface material and a shape surrounding the periphery of the layered portion And the layered portion is composed of a cured product of the curable resin composition of claim 1. A laminate having: a pair of face materials; and an adhesive layer disposed between the face materials and facing the two faces facing each other; The adhesive layer has a layered portion extending along the surface of the face material and a weir portion surrounding the periphery of the layered portion; and the layered portion is composed of a cured product of the curable resin composition of claim 1. A laminated body comprising: a pair of face materials; and an adhesive layer disposed between the face materials and facing opposite faces; the adhesive layer has a layered portion extending along a surface of the face material; The layered portion is composed of a cured product of the curable resin composition of claim 1. The laminate of claim 9 or 10, wherein one of the pair of face materials is a display panel. A laminate which is formed by hardening a curable resin composition as claimed in claim 1.