TWI575041B - Adhesive, laminate and methods of producing same - Google Patents

Description

Subsequent agent, laminate, and manufacturing method of the foregoing

The present invention relates to an adhesive, a laminate, and a method of producing the foregoing.

Various binders are used in order to follow an inorganic material such as a metal or a metal oxide and an organic material such as a resin. However, an adhesive such as an acrylic resin generally used is followed by an intermolecular force and an inorganic material, and thus a sufficiently strong adhesive force may not be obtained. Therefore, an adhesive capable of adhering more closely to inorganic materials and organic materials has been sought.

In the related art, Japanese Laid-Open Patent Publication No. 2012-116895 discloses the use of a photocurable adhesive comprising a cellulose derivative and a photocurable medium with a decane coupling agent and a surfactant to make a glass as an inorganic material and an organic material. The triacetyl cellulose is then carried on. Furthermore, it is described that a cellulose derivative having a hydroxyalkyl group as a cellulose derivative can improve the adhesion of an adhesive, and it is described that the decane coupling agent can be further improved. The viewpoint of the adhesion of the adhesive film formed by the adhesive to the substrate is thus used.

Japanese Laid-Open Patent Publication No. Hei 6-145201 discloses a cellulose derivative containing a siloxane having both properties of cellulose and anthrone and a method for producing the same. It is also described that the above-mentioned oxoxane-containing cellulose derivative is also useful as an adhesive.

However, the cellulose derivative and the decane coupling agent are each contained in the monomer described in JP-A-2012-116895, and the two do not form a chemically bonded structure. Further, the decane coupling agent is not in a polymer state, and it is considered that the adhesion to the inorganic material is limited. The oxime portion of the oxoxane-containing cellulose derivative described in JP-A-6-145201 does not have a functional group reactive with a hydroxyl group present on the surface of the inorganic material, and is considered not to be carried out with an inorganic material. Chemical bonding. Further, the oxane portion is not in a polymer state, and it is considered that the adhesion to the inorganic material is limited. The present invention has been made in view of the above circumstances, and an object thereof is to provide an adhesive which exhibits excellent adhesion to both an inorganic material and an organic material, a laminate using the same, and a production method therefor.

The following are means to achieve the aforementioned objectives.

<1> An adhesive comprising a condensate of a cellulose derivative and a polyoxyalkylene having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group.

(2) The adhesive agent according to the above, wherein the polyoxysilane has an average value of a total number of substituents selected from at least one of a group consisting of a hydroxyl group and an alkoxy group. Each one of the germanium atoms is 0.5 or more.

<3> The adhesive according to <1> or <2>, wherein the cellulose derivative comprises a structural unit derived from glucose, and the structural unit derived from glucose has a group selected from the group consisting of an alkyl group and a mercapto group. In the case of at least one of the substituents, the average value of the total number of the substituents is 1.0 or more of the structural unit derived from glucose.

The adhesive agent according to any one of <1> to <3>, further comprising an organic solvent, wherein the organic solvent contains at least one selected from the group consisting of an ether solvent, a ketone solvent, and an ester solvent. .

<5> A method for producing an adhesive, which is produced by any one of <1> to <4> And a mixture comprising a cellulose derivative and a polyoxyalkylene having a substituent selected from the group consisting of a hydroxyl group and an alkoxy group, wherein the cellulose derivative is obtained by heating The condensate of the aforementioned polyoxyalkylene.

<6> The method for producing an adhesive according to <5>, further comprising a decane compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group, water, and an organic solvent. In the solution, the decane compound is subjected to hydrolysis and polycondensation to obtain a polyoxyalkylene having a substituent selected from at least one selected from the group consisting of a hydroxyl group and an alkoxy group.

<7> The method for producing an adhesive according to <6>, wherein the mass ratio of the decane compound to the cellulose derivative is 1:9 to 9:1.

<8> The method for producing an adhesive according to <6>, wherein the solution containing a decane compound, water, and an organic solvent further contains an acidic catalyst.

<9> A laminate comprising a first layer and a second layer containing at least one of the inorganic materials, using the adhesive according to any one of <1> to <4> or using, for example, <5> The adhesive produced by the method for producing an adhesive according to any one of <8> is followed by the structure.

<10> The laminate according to <9>, wherein one of the first layer and the second layer contains an inorganic material, and the other contains an organic material.

The laminate according to the above aspect, wherein the inorganic material contains at least one selected from the group consisting of a metal and a metal oxide.

The laminate according to the <10>, wherein the organic material is selected from the group consisting of a cellulose resin, a polyimide resin, a polyamide resin, and a polyester resin. At least one of them.

<13> A method of producing a laminate according to any one of <9> to <12> And the production of the adhesive agent according to any one of <1> to <4> or the adhesive agent according to any one of <5> to <8>. The adhesive layer of the adhesive produced by the method is combined with the second layer, and the first layer and the second layer are followed.

The method for producing a laminate according to the above aspect, wherein the step of applying the heat and the pressure is performed.

According to the present invention, it is possible to provide an adhesive which exhibits excellent adhesion to both an inorganic material and an organic material, a laminate using the same, and a method for producing the both.

1‧‧‧Triacetyl cellulose (TAC) film 1

2‧‧‧glass plate

3‧‧‧Triacetyl cellulose (TAC) film 3

Fig. 1 is an electron micrograph showing an example of a cross-sectional structure of a laminate of the present invention.

In this specification, the term "step" means not only an independent step, but even if it cannot be clearly distinguished from other steps, it is included in the term as long as the intended purpose of the step can be achieved. In addition, in the present specification, the numerical range indicated by "~" indicates the range including the numerical values described before and after "~" as the minimum value and the maximum value. Furthermore, in the present specification, the amount of each component in the composition is such that when the composition conforms to the majority of the substances of the components, unless otherwise specified, it means that the composition exists. The total amount of most substances.

<Binder>

The adhesive of the present invention comprises a condensate of a cellulose derivative and a polyoxyalkylene having a substituent selected from at least one selected from the group consisting of a hydroxyl group and an alkoxy group (hereinafter also referred to as a specific condensate). . The above-mentioned adhesive agent exhibits excellent adhesion to both the inorganic material and the organic material, and can firmly adhere to the inorganic material and the organic material. The reason is believed to be as follows.

The polyoxyalkylene moiety of the specific condensate has a substituent selected from at least one of a group consisting of a hydroxyl group and an alkoxy group, and is chemically bonded to a hydroxyl group present on the surface of the inorganic material. Knot. Thereby, it is considered that an adhesion force which is stronger than the adhesion force by the intermolecular force can be obtained. Further, it is considered that the siloxane unit is continuously in a state of being a polymer, and therefore there are many reaction points with the hydroxyl group present on the surface of the inorganic material, and the adhesion force with the inorganic material becomes stronger. Further, it is considered that the cellulose derivative portion of the specific condensate has high affinity with the organic material, so that a strong adhesive force with the organic material can be obtained.

The polyoxyalkylene moiety of the specific condensate has at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group, from the viewpoint of obtaining a strong adhesive force with the inorganic material. It is desirable that the ruthenium atoms bonded to the siloxane unit have an optimum number. Specifically, the average value of the total number of substituents selected from at least one of the group consisting of a hydroxyl group and an alkoxy group bonded to a halogen atom contained in the polyoxyalkylene moiety of the specific condensate It is preferably 0.5 or more, more preferably 0.7 or more, and still more preferably 1.0 or more per one atom.

The alkoxy group may, for example, be an alkoxy group having 1 to 10 carbon atoms. The aforementioned alkoxy group may have a substituent. The alkoxy group is preferably a methoxy group, an ethoxy group, a propoxy group or a butoxy group, more preferably a methoxy group or an ethoxy group, and still more preferably a methoxy group. The substituent of at least one selected from the group consisting of a hydroxyl group and an alkoxy group in the polyoxyalkylene moiety of the specific condensate may be one type or two or more types.

The weight average molecular weight of the polyoxyalkylene moiety of the specific condensate is not particularly limited, and is preferably from 60 to 100,000, more preferably from 100 to 80,000, still more preferably from 600 to 60,000.

The cellulose derivative portion of the specific condensate preferably contains a structural unit derived from glucose, and the structural unit derived from glucose has at least one substituent selected from the group consisting of an alkyl group and a mercapto group. From the viewpoint of solubility in a solvent contained in the adhesive, it is preferred that each of the structural units derived from glucose is selected from at least one substituent selected from the group consisting of an alkyl group and a fluorenyl group. The average value of the total number is 1.0 or more, more preferably 1.5 or more, and still more preferably 2.0 or more.

The alkyl group may, for example, be an alkyl group having 1 to 10 carbon atoms. The alkyl group may have a substituent, and examples of the substituent include a hydroxyl group and a carboxyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, a hydroxyethyl group or a hydroxypropyl group, and still more preferably a methyl group or an ethyl group. Examples of the sulfhydryl group include a fluorenyl group having 1 to 10 carbon atoms. The fluorenyl group is preferably a fluorenyl group having 1 to 4 carbon atoms, more preferably a fluorenyl group, an ethyl fluorenyl group, a propyl fluorenyl group or a butyl group, and more preferably an acetamino group. The substituent of at least one selected from the group consisting of an alkyl group and a fluorenyl group in the cellulose derivative portion of the specific condensate may be one type or two or more types.

The weight average molecular weight of the cellulose derivative portion of the specific condensate is not particularly limited, and is preferably from 1,000 to 500,000, more preferably from 5,000 to 100,000, still more preferably from 10,000 to 50,000.

The condensation state of the cellulose derivative portion of the specific condensate with the polyoxymethane portion is not particularly limited, and it is preferred that the cellulose derivative portion contains the structural unit derived from glucose and the polyoxymethane portion. The contained ruthenium atoms are bonded via at least an oxygen atom.

The specific condensate is desirably a structural unit represented by the following formula (1).

In the formula, R ¹ represents a hydrogen atom or an alkyl group, and R ² and R ³ each independently represent a hydrogen atom, an alkyl group or a fluorenyl group. Most of the existing R ¹ , R ² and R ³ may be the same or different from each other.

The alkyl group represented by R ¹ may, for example, be an alkyl group having 1 to 10 carbon atoms. The aforementioned alkyl group may also have a substituent. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group or a butyl group, still more preferably a methyl group or an ethyl group.

The alkyl group represented by R ² and R ³ may, for example, be an alkyl group having 1 to 10 carbon atoms. The alkyl group may have a substituent, and examples of the substituent include a hydroxyl group and a carboxyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, a hydroxyethyl group or a hydroxypropyl group, and still more preferably a methyl group or an ethyl group.

Examples of the fluorenyl group represented by R ² and R ³ include a fluorenyl group having 1 to 10 carbon atoms. The fluorenyl group is preferably a fluorenyl group having 1 to 4 carbon atoms, more preferably a fluorenyl group, an ethyl fluorenyl group, a propyl fluorenyl group or a butyl group, and more preferably an acetamino group.

In the specific condensate, in the formula (1), R ¹ is preferably a hydrogen atom or a methyl group, and at least one of R ² and R ^{3 is} a structure containing an ethyl fluorenyl group, and more preferably R ¹ is a hydrogen atom or a group. The base, R ² and R ³ respectively contain a structure of an ethyl fluorenyl group.

The weight average molecular weight of the specific condensate is not particularly limited, and is preferably 2,000 to 600,000, more preferably 3,000 to 200,000, still more preferably 5,000 to 50,000.

The mass ratio of the polyoxyalkylene moiety to the cellulose derivative portion of the specific condensate (polyoxyalkylene moiety: cellulose derivative moiety) is not particularly limited, from the viewpoint of obtaining good adhesion, The best is 1:9~9:1, more preferably 2:8~8:2, and even better 3:7~7:3.

In particular, if the mass ratio of the polyoxyalkylene moiety to the cellulose derivative portion of the specific condensate is in the range of 3:7 to 7:3, a good adhesion can be obtained while a soft structural condensation can be obtained. The tendency of things. Such a property is advantageous in the case where an adhesive is applied to an adherend having a flexible substance.

The content of the specific condensate in the adhesive of the present invention is not particularly limited, but is preferably 1% by mass to 90% by mass, more preferably 1% by mass to 50% by mass, still more preferably 5% by mass to 30% by mass. .

The adhesive of the present invention may further contain components other than the specific condensate. Specific examples thereof include an organic solvent, water, a decane compound which does not constitute a specific condensate, and a cellulose derivative.

The organic solvent is not particularly limited as long as it can dissolve or disperse a specific condensate. Specific examples thereof include ketone solvents such as cyclohexanone, acetone, methyl ethyl ketone, and diethyl ketone, methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tertiary alcohol. Alcohol solvent such as butanol, halogenated hydrocarbon solvent such as chloroform or dichloromethane; aromatic hydrocarbon solvent such as benzene or toluene; ester solvent such as ethyl acetate, butyl acetate or isopropyl acetate; diethyl ether, tetrahydrofuran, An ether solvent such as an alkane, a glycol ether solvent such as ethylene glycol monomethyl ether or ethylene glycol dimethyl ether, or the like. The organic solvent is preferably a ketone solvent, an ether solvent or an ester solvent.

From the viewpoint of obtaining a strong adhesive force with an organic material, an ideal adhesive is an organic solvent which moderately dissolves the surface of the organic material upon contact with the organic material. For example, when the organic material contains a cellulose derivative such as triacetyl cellulose, it preferably contains at least one ether solvent, more preferably two. alkyl.

An organic solvent can also be selected from the viewpoint of enhancing the applicability of the adhesive to the substrate. For example, from the viewpoint of uniformly applying the adhesive to the surface of the substrate to be attached, it is preferred to include at least one selected from the group consisting of a ketone solvent, an ester solvent, and an ether solvent, and more preferably an optional one. It is more preferable to contain cyclohexanone from at least one of the group consisting of a ketone solvent and an ester solvent.

The organic solvent may be used singly or in combination of two or more. The organic solvent may be composed of, for example, only a solvent used for synthesis of a specific condensate, or may be combined with other solvents.

The boiling point of the organic solvent is not particularly limited, and is preferably from 40 ° C to 250 ° C, more preferably from 45 ° C to 200 ° C, still more preferably from 50 ° C to 160 ° C.

The content of the organic solvent is not particularly limited, but is preferably from 1% by mass to 99% by mass, more preferably from 50% by mass to 99% by mass, even more preferably from 70% by mass to 95% by mass in the adhesive.

<Method of Manufacturing Adhesive Agent>

The method for producing an adhesive of the present invention comprises the steps of: a cellulose derivative having a polyoxyalkylene having a substituent selected from at least one selected from the group consisting of a hydroxyl group and an alkoxy group (hereinafter also A mixture called a specific polyoxane is heated to obtain a specific condensate.

An ideal value of a specific polyoxyalkylene having a substituent selected from at least one of a group consisting of a hydroxyl group and an alkoxy group, and an ideal type of an alkoxy group, and a polycondensation of the above specific condensate The average value of each of the ruthenium atoms selected from the total number of the substituents selected from the group consisting of a hydroxyl group and an alkoxy group, and the desired type of the alkoxy group are the same. . The substituent of at least one selected from the group consisting of a hydroxyl group and an alkoxy group, which is a specific polysiloxane, may be used alone or in combination of two or more.

The weight average molecular weight of the specific polyoxyalkylene is not particularly limited, and is preferably from 60 to 100,000, more preferably from 100 to 80,000, still more preferably from 600 to 60,000.

The specific polyoxyalkylene can also be used commercially, or can be produced by a method described later.

The cellulose derivative is not particularly limited, and from the viewpoint of reacting with a specific polyoxyalkylene to form a specific condensate, it is preferred that the cellulose derivative has a hydroxyl group. From the viewpoint of solubility in a solvent, it is preferred that the cellulose derivative has a substituent other than a hydroxyl group. Therefore, it is preferred that the cellulose derivative has a hydroxyl group and a substituent other than a hydroxyl group. The substituents other than the hydroxyl group of the cellulose derivative may be used alone or in combination of two or more.

Examples of the substituent other than the hydroxyl group of the cellulose derivative include an alkyl group and a decyl group. The alkyl group may have a more substituent, and examples of the substituent include a hydroxyl group and a carboxyl group.

The alkyl group may, for example, be an alkyl group having 1 to 10 carbon atoms. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, a hydroxyethyl group or a hydroxypropyl group, and still more preferably a methyl group or an ethyl group.

Examples of the sulfhydryl group include a fluorenyl group having 1 to 10 carbon atoms. The fluorenyl group is preferably a fluorenyl group having 1 to 4 carbon atoms, more preferably a fluorenyl group, an ethyl fluorenyl group, a propyl fluorenyl group or a butyl group, and more preferably an acetamino group.

The substituent other than the hydroxyl group of the cellulose derivative is preferably at least one selected from the group consisting of an alkyl group and a mercapto group, more preferably an anthracenyl group, and still more preferably an ethylidene group.

Examples of the cellulose derivative having a substituent other than a hydroxyl group and a hydroxyl group include cellulose ether compounds such as methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, and hydroxyethyl group, and ethyl cellulose, and A cellulose ester compound such as acetaminophen, cellulose acetate butyrate or cellulose acetate propionate. The cellulose derivative is preferably a cellulose ester compound, more preferably diethyl cellulose.

From the viewpoint of allowing the cellulose derivative to react with a specific polyoxane at a good efficiency, the cellulose derivative has a larger number of hydroxyl groups as much as possible. On the other hand, from the viewpoint of solubility in an organic solvent, the number of substituents other than the hydroxyl group contained in the cellulose derivative is preferably as large as possible. In view of the above, the degree of substitution of the cellulose derivative (the average of the number of substitutions among the three hydroxyl groups in the structural unit derived from glucose) is preferably from 1.0 to 2.5, more preferably from 1.0 to 2.0.

The weight average molecular weight of the cellulose derivative is not particularly limited, and is preferably from 1,000 to 500,000, more preferably from 5,000 to 100,000, still more preferably from 10,000 to 50,000.

The mass ratio of the specific polyoxyalkylene to the cellulose derivative (specific polyoxyalkylene: cellulose derivative) contained in the mixture of the specific polyoxyalkylene and the cellulose derivative is not particularly limited, and good adhesion is obtained. From the viewpoint, it is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3.

In particular, when the mass ratio of the specific polyoxyalkylene to the cellulose derivative is in the range of 3:7 to 7:3, there is a tendency that a good condensate of a soft structure can be obtained while obtaining a good adhesion. Such a property is advantageous when the adhesive is applied to a case having a flexible material.

A mixture comprising a specific polyoxane and a cellulose derivative, desirably further comprising an organic solvent. The organic solvent can also be selected, for example, from an organic solvent suitable for the above-mentioned adhesive. When a specific polyoxyalkylene is used for the preparation, it can also be selected from organic solvents suitable for the preparation of a specific polyoxyalkylene.

A mixture of a specific polyoxyalkylene and a cellulose derivative is desirably contained as a catalyst from the viewpoint of condensation at a good efficiency. The type of the catalyst is not particularly limited, and may be an acidic catalyst or an alkaline catalyst. Examples of the acidic catalyst include organic acids and inorganic acids. The inorganic acid may, for example, be hydrogen halide such as hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide or carbonic acid. The organic acid may, for example, be a carboxylic acid such as formic acid or acetic acid or a sulfonic acid such as benzenesulfonic acid. Examples of the basic catalyst include an ammoniacal base such as ammonia water, an organic amine such as ethylamine or aniline, and the like. The catalyst is preferably an acidic catalyst, more preferably an inorganic acid, more preferably hydrochloric acid, nitric acid or phosphoric acid, and particularly preferably hydrochloric acid. The amount of the catalyst to be added is not particularly limited, and is preferably 0.01% to 10.00%, more preferably 0.10% to 0.50%, based on the mass of the specific polyoxyalkylene.

The conditions for obtaining a specific condensate by heating a mixture containing a specific polyoxyalkylene and a cellulose derivative are not particularly limited, and it is preferably stirred at 40 ° C to 60 ° C for 10 minutes to 180 minutes, more preferably at 40 ° C. Stir at 60 ° C for 60 minutes to 120 minutes. The content of the specific polyoxyalkylene in the mixture containing the specific polyoxyalkylene and the cellulose derivative is not particularly limited, and may be, for example, 0.1% by mass to 30.0% by mass in the mixture. The content of the cellulose derivative in the mixture containing the specific polyoxyalkylene and the cellulose derivative is not particularly limited, and may be, for example, 2.0% by mass to 20.0% by mass in the mixture.

The solution after the formation of the specific condensate may also be used as an adhesive directly, or may be used by concentration or dilution.

(Preparation of specific polyoxyalkylene)

The specific polyoxyalkylene can be produced by hydrolysis and polycondensation of a decane compound (hereinafter also referred to as a specific decane compound) having a substituent selected from at least one selected from the group consisting of a hydroxyl group and an alkoxy group. As a method of preparing a specific polyoxyalkylene by hydrolysis and polycondensation of a specific decane compound, for example, a sol-gel method or the like can be mentioned. Specifically, a specific polyoxyalkylene can be obtained by subjecting a specific alkoxydecane to hydrolysis and polycondensation in a solution containing a specific decane compound, water, and an organic solvent.

In the case where a specific polyoxyalkylene is produced by hydrolysis and polycondensation of a specific decane compound, the obtained specific polyoxyalkylene can also be mixed with a cellulose derivative to obtain a specific condensate. The method of mixing the specific polyoxyalkylene and the cellulose derivative is not particularly limited. For example, the cellulose derivative may be directly added to a specific polyoxyalkylene or may be mixed with a solution of the dissolved cellulose derivative in a solvent.

The specific decane compound is not particularly limited as long as it has at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group, but is included in a specific polymerization from the viewpoint of the adhesion of the adhesive to the inorganic material. The greater the number of substituents selected from at least one of the group consisting of a hydroxyl group and an alkoxy group in the oxane, the better. Therefore, the number of substituents selected from at least one selected from the group consisting of a hydroxyl group and an alkoxy group contained in a specific decane compound is preferably as large as possible. Specifically, the average value of the number of substituents selected from at least one selected from the group consisting of a hydroxyl group and an alkoxy group in a specific decane compound is preferably 1.0 or more, and more preferably 2.0 or more. More preferably, it is 3.0 or more.

The kind of the substituent selected from at least one selected from the group consisting of a hydroxyl group and an alkoxy group, which is contained in a specific decane compound, is not particularly limited, and is preferably selected from the group consisting of a hydroxyl group and an alkoxy group. At least one of the substituents of at least one of them is a methoxy group or an ethoxy group, more preferably a methoxy group. The aforementioned alkoxy group may be further substituted with other substituents. The specific decane compound may have a substituent other than the substituent selected from the group consisting of a hydroxyl group and an alkoxy group, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms. The alkyl group may have a more substituent group, and examples of the substituent include an alkoxy group having 1 to 10 carbon atoms.

Specific examples of the specific decane compound include dioxane such as dimethyldimethoxydecane, diethyldimethoxydecane, dimethyldiethoxydecane, and diethyldiethoxydecane. Trioxane such as oxydecane, methyltrimethoxydecane, ethyltrimethoxydecane, methyltriethoxydecane, ethyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane Oxydecane, tetramethoxynonane, tetraethoxydecanetetraalkoxydecane, and the like. The specific decane compound is preferably a tetraalkoxy decane, more preferably tetraethoxy decane or tetramethoxy decane.

The organic solvent for dissolving the specific decane compound is not particularly limited, and is preferably an alcohol solvent, an ether solvent or a ketone solvent from the viewpoint of promoting the hydrolysis reaction and the polycondensation reaction, more preferably an ether solvent, and even more preferably two. alkyl. The organic solvent may also be selected from organic solvents suitable for the above-mentioned adhesives.

From the viewpoint of promoting hydrolysis and polycondensation of a specific decane compound, it is desirable to use a catalyst. The type of the catalyst is not particularly limited, and may be an acidic catalyst or an alkaline catalyst. Examples of the acidic catalyst include organic acids and inorganic acids. The inorganic acid may, for example, be hydrogen halide such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide or carbonic acid. The organic acid may, for example, be a carboxylic acid such as formic acid or acetic acid or a sulfonic acid such as benzenesulfonic acid. Examples of the basic catalyst include an ammoniacal base such as ammonia water, an organic amine such as ethylamine or aniline, and the like. The amount of the catalyst to be added is not particularly limited, and is preferably 0.01% to 10.00% of the mass of the specific polyoxane.

The type of the catalyst is not particularly limited, but the basic catalyst tends to be polycondensed in a block shape, and the acidic catalyst tends to cause the polycondensation to proceed to a linear shape. Therefore, from the viewpoint of improving the efficiency of condensation of the specific polysiloxane and the cellulose derivative obtained, an acidic catalyst, more preferably an inorganic acid, more preferably hydrochloric acid is preferred. The catalyst may be used alone or in combination of two or more. The catalyst may be directly added to a solution containing a specific decane compound, or may be added in a state of being dissolved in a solvent.

The conditions for subjecting the specific decane compound to hydrolysis and polycondensation are not particularly limited, and may be selected from known methods.

<Laminated body>

The laminate of the present invention comprises a structure in which at least one of the first layer and the second layer containing an inorganic material is obtained by using the adhesive of the present invention.

The first layer and the second layer may be a combination of a layer containing an inorganic material and a layer containing an inorganic material, or a combination of a layer containing an inorganic material and a layer containing an organic material. The laminate may have a structure of three or more layers including another layer.

The effect of the adhesive of the present invention which exhibits a high adhesion force between both the inorganic material and the organic material is apparent when the layer containing the inorganic material is followed by the layer containing the organic material. In particular, when a clear interface is not formed between the adhesive and the layer containing the organic material, and the adhesive and the organic material are integrated, a stronger adhesive force can be obtained.

Fig. 1 is an electron micrograph showing an example of a state in which an adhesive of the present invention is integrated with an organic material. Specifically, it is shown that a layer having a thickness of 10 μm to 15 μm composed of the adhesive of the present invention is formed on both surfaces of a glass plate 2 having a thickness of 70 μm, and a triacetonitrile cellulose (TAC) having a thickness of 40 μm is disposed thereon. The laminates of the laminates 1 and 3 were obtained by thermocompression bonding. As shown in Fig. 1, it is observed that the glass plate 2 and the TAC films 1 and 3 are in a state in which the layer of the adhesive is not interposed. The reason why such an adhesive is integrated with the organic material is not known, but it is presumed that, for example, the molecules of the adhesive enter the resin molecules constituting the TAC film.

The inorganic material is not particularly limited as long as it is a material having a hydroxyl group which can react with a hydroxyl group or an alkoxy group which the azide moiety of the specific condensate has on the surface. Specifically, a metal, a metal oxide, etc. are mentioned, for example.

The type of the metal is not particularly limited, and examples thereof include a semimetal such as iron, aluminum, copper, or ruthenium, an alloy containing the metals, and the like. The type of the metal oxide is not particularly limited, and examples thereof include the above-described metal oxides. Among them, the inorganic material is particularly preferably a glass containing a metal oxide. Examples of the type of the glass include quartz, sodium borosilicate glass, organic-inorganic hybrid glass, and the like.

The organic material is not particularly limited as long as it has a high affinity with the cellulose derivative portion of the specific condensate. Specific examples thereof include a cellulose resin such as triacetonitrile cellulose, a polyamide resin, a polyimide resin, and a polyester resin. In particular, from the viewpoint of affinity with an adhesive, a cellulose resin is preferred, and triethylenesulfonate is more preferred.

The thickness of the first layer and the second layer in the laminate of the present invention is not particularly limited and may be selected depending on the application. The adhesive of the present invention can exhibit excellent adhesion regardless of the thickness of the layer constituting the laminate. Strength.

<Method of Manufacturing Laminates>

The method for producing a laminate of the present invention comprises the steps of: arranging a first layer, an adhesive layer comprising the adhesive of the present invention, and a second layer in this order, and at least one of the first layer and the second layer Contains inorganic materials.

In the laminate, an adhesive may be applied to any of the first layer and the second layer to form an adhesive layer, and another layer may be disposed on the formed adhesive layer to be manufactured. An adhesive may be applied to the first layer and the second layer to form an adhesive layer, and the formed adhesive layers may be bonded to each other to be produced. Further, the above steps may be repeated to produce a laminate of three or more layers.

The method of forming the adhesive layer on at least one of the first layer and the second layer is not particularly limited. Specific examples thereof include a spinning method, a brush coating method, a spray method, a doctor blade method, a roll coating method, and an inkjet method. The subsequent layer may be formed by applying an adhesive to at least one of the first layer and the second layer, and then applying at least a portion of the solvent contained in the adhesive layer by heating or the like. Formed by removal. The thickness of the subsequent agent layer is not particularly limited and may be, for example, 0.01 μm to 100 μm.

From the viewpoint of improving the adhesion to the first layer and the second layer of the adhesive layer, it is also possible to apply the first layer, the adhesive layer, and the second layer in this order, and then apply heat or pressure to the adhesive layer at least. One. The heat or pressure to be applied is not particularly limited, and varies depending on the material, thickness, and the like of the adhesive, the first layer, and the second layer. For example, when an adhesive layer is formed on one surface of a glass plate having a thickness of 30 μm to 100 μm, and a heat and pressure are applied to a triethylene fluorene cellulose film having a thickness of 0.1 μm to 50 μm, Next, a triethylene fluorene cellulose film is placed on the agent layer, and then heated and pressurized at 50 ° C to 150 ° C and 0.01 Pa to 1 MPa for 5 minutes to 120 minutes.

The first layer and the second layer may be prepared before the production of the laminate, or may be formed using the materials of the layers during the production of the laminate. For example, it is also possible to apply the layers of the material to the temporary support or the formed adhesive layer in the same manner as the application of the adhesive, and Drying or the like is carried out to thereby form the layers.

<Flexible substrate>

The laminate produced by using the adhesive of the present invention can be preferably used for a flexible substrate such as a flexible display, an electronic paper, a flexible illumination, or a flexible solar cell.

For example, it is considered to be applicable to a flexible substrate which is provided with a gas barrier property by attaching an ultrathin plate glass having a thickness of about 30 μm to 150 μm on a polarizing film of a liquid crystal display using an organic film such as a triacetyl cellulose film. Manufacturing. A flexible substrate for producing a gas transmission rate (10 ^-6 to 10 ^-4 g/m ² /d) necessary for a conventional flexible substrate must be vacuum-deposited or splashed on the organic film. The inorganic thin film is laminated on 4 to 6 layers by plating. On the other hand, according to the present invention, it is possible to manufacture a flexible substrate having a performance superior to that of a flexible substrate in which an inorganic thin film is laminated, by attaching an organic film to an ultrathin glass. In addition, when the ultrathin plate glass having a thickness of about 30 μm to 150 μm is attached to the triacetonitrile cellulose film, the gas permeability is substantially zero, and gas barrier properties equivalent to those of a display using a normal glass substrate can be obtained.

In general, the smaller the thickness of the layer containing the inorganic material, the more the flexibility tends to be increased, but the material may be brittle depending on the material to reduce the flexibility. If such a material subsequently comprises a layer of an organic material, there is a case where the brittleness of the layer containing the inorganic material is improved and the flexibility is improved. When the flexible substrate contains a layer containing an inorganic material and a layer containing an organic material, the thickness of the layer containing the inorganic material is not particularly limited, and may be, for example, 200 μm or less, or may be 10 μm to 200 μm. The thickness of the layer containing the organic material is not particularly limited and may be, for example, 250 μm or less, or may be 10 μm to 250 μm. The total thickness of the flexible substrate is not particularly limited and may be, for example, 500 μm or less, or may be 20 μm to 500 μm.

When the flexible substrate is used in a display or the like, it must have high transparency. The adhesive of the present invention has high transparency and hardly affects the transparency of the flexible material produced using the film.

The adhesive of the present invention is also effective as a means for improving the flexibility of a material having poor flexibility. Therefore, for example, the adhesive of the present invention can also be suitably used for laminating a resin film. In the production of ultra-thin sheet glass which is flexible, or the addition of two or more sheets of ultra-thin sheet glass, the adhesive itself is used as a resin film to enhance the production of flexible ultra-thin glass.

[Examples]

Hereinafter, the present invention will be described in more detail by reference to examples, but the invention is not limited to the examples. Furthermore, "%" is a quality benchmark.

<Example 1>

(Preparation of specific polyoxyalkylene)

1.095 g (7.19 mmol) of tetramethoxy decane (TMOS, manufactured by Shin-Etsu Chemical Co., Ltd.) and 5.000 g of 1,4-two were weighed. An alkane (manufactured by Kanto Chemical Co., Ltd.) to a 30 ml spiral tube was stirred with a magnetic stirrer to dissolve tetramethoxysilane. Thereafter, while continuing to stir, slowly add 1,4-two with 1.500 g A solution of 0.034 g of 12 mol/L hydrochloric acid (manufactured by Kanto Chemical Co., Ltd.) was diluted with alkane. Further, slowly add 1.840 g of 1,4-two A solution of 0.530 g of pure water diluted with alkane. Thereafter, the mixture was stirred under heating in a water bath at 60 ° C for 2 hours.

A specific polyoxane (TMOS sol) was prepared by the above procedure.

(Preparation of specific condensate)

3.00 g of diacetyl cellulose (DAC, manufactured by Kanto Chemical Co., Ltd., polymerization degree 150) and 15.90 g of 1,4-two were weighed. The alkane was transferred to a 30 ml spiral tube and stirred with a magnetic stirrer to dissolve the diethyl cellulose. To this DAC solution, a previously prepared sol solution of 8.100 g of a specific polyoxyalkylene was further added and further stirred under heating in a water bath at 60 ° C for 2 hours. After stirring for 2 hours, 3.000 g of cyclohexanone was added to the reaction solution.

By the above operation, a solution of a specific condensate (TMOS-DACsol) was prepared. The mass ratio of TMOS solution to DAC solution (TMOS: DAC) was set at 3:7.

(production of laminate)

An ultrathin plate glass (50 mm × 40 mm) having a thickness of 70 μm was placed on an applicator table, and a small amount of the above-mentioned solution of the specific condensate was dropped on the top of the ultrathin plate glass, and a TAC film having a thickness of 100 μm was placed thereon. Fix the TAC film with tape to keep it from moving. Apply the applicator from the TAC film. The surface is slowly moved from one end of the ultrathin plate glass to the other end at a certain speed so that the specific condensate solution is extruded and the TAC film is closely adhered. The ultrathin plate glass which has been closely adhered to the TAC film was turned over, and a TAC film having a thickness of 100 μm was closely attached to the other side of the ultrathin plate glass in the same manner as described above. Thereafter, prebake was performed in a dryer at 80 ° C for 10 minutes, and then subjected to heat and pressure treatment for 30 minutes under conditions of 100 ° C and 0.1 MPa to adhere the TAC film to the ultrathin plate glass.

As described above, a laminate of TAC films each having a thickness of 100 μm on both surfaces of the ultrathin plate glass was produced. A laminate in which the thickness of the TAC film was changed to 40 μm, 60 μm, and 80 μm was also produced in the same manner.

<Example 2>

A solution of a specific condensate having a DAC concentration of 7.5% was prepared in the same manner as in Example 1 except that the amount of the DAC was changed. A laminate of the obtained specific condensate was used in the same manner as in Example 1 to prepare a laminate. A laminate in which the thickness of the TAC film was changed to 40 μm, 60 μm, and 80 μm was also produced in the same manner.

<Example 3>

A solution of a specific condensate having a DAC concentration of 5.0% was prepared in the same manner as in Example 1 except that the amount of the DAC was changed. A laminate was produced in the same manner as in Example 1 using the obtained solution of the specific condensate. A laminate in which the thickness of the TAC film was changed to 40 μm, 60 μm, and 80 μm was also produced in the same manner.

<Example 4>

A solution of a specific condensate having a DAC concentration of 2.5% was prepared in the same manner as in Example 1 except that the amount of the DAC was changed. A laminate was produced in the same manner as in Example 1 using the obtained solution of the specific condensate. A laminate in which the thickness of the TAC film was changed to 40 μm, 60 μm, and 80 μm was also produced in the same manner.

<Example 5>

Executed in the same manner as in the first embodiment except that the amount of DAC and TMOS was changed, A solution of a specific condensate having a mixing ratio of TMOS to DAC (TMOS: DAC) of 5:5 was prepared. The DAC concentration was 2.5%. A laminate was produced in the same manner as in Example 1 except that the thickness of the TAC film on both surfaces of the ultrathin glass was changed to 60 μm.

<Example 6>

A solution of a specific condensate having a mixing ratio of TMOS to DAC (TMOS: DAC) of 7:3 was prepared in the same manner as in Example 1 except that the amounts of DAC and TMOS were changed. The DAC concentration was 2.5%. A laminate was produced in the same manner as in Example 1 except that the thickness of the TAC film on both surfaces of the ultrathin glass was changed to 60 μm.

<Evaluation of transparency>

The Luminous transmittance of the laminates produced in Examples 1 to 6 in the visible light range was measured by an ultraviolet-visible spectrophotometer. As a result of the measurement, all of Examples 1 to 6 were 90% or more in the range of wavelengths of 400 nm to 800 nm, and it was confirmed that the transparency was extremely high.

<Continue evaluation of force>

The adhesion of the solution of the specific condensate prepared in Examples 1 to 6 to the glass substrate and the TAC film was evaluated by a checkerboard test prescribed in JIS-K5400. Specifically, tests were carried out on the coating film formed in the following manner: a solution of the specific condensate prepared in Examples 1 to 6 was applied onto the glass substrate and the TAC film by an applicator, and dried at 100 ° C. The coating film is formed in minutes. As a result, the number of peeling sheets in 25 cells was all 0, and it was confirmed that the adhesion to the glass substrate and the TAC film was very high. For comparison, a checkerboard test was performed by forming a coating film of a DAC unit on a glass substrate. As a result, all of the 25 cells were peeled off, and it was confirmed that the adhesion to the glass substrate was inferior.

<Evaluation of flexibility>

For the laminates produced in Examples 1 to 6, the torsional strength test was carried out in accordance with the following method.

A double-sided tape was attached to both surfaces of the end portion on the side of the laminate having a length of 50 mm, and a slide glass (thickness: 1 mm) was attached thereto, and a slip-resistant tape was attached thereto to obtain a sample for evaluation. Will receive comments The two ends of the slide glass of the sample for the valence sample were respectively clamped and fixed by two devices having an arm portion capable of sandwiching the end portion. Thereafter, the arm portion of the device was gradually rotated to twist the laminate, and the angle at which the ultra-thin glass of the laminate was cracked was measured as the twist angle. The results are shown in Table 1. As a comparative example, the torsion angle of the ultrathin plate glass monomer (without the TAC film) used in the examples was measured.

As shown in the results of Table 1, the TAC film was bonded to the laminate of Examples 1 to 6 of the ultrathin plate glass, and cracking did not occur until the twist angle was about 40° or more. On the other hand, the ultrathin plate glass of the comparative example was cracked at a torsion angle of 17.2°. From the above results, it was found that the flexibility of the ultra-thin plate glass can be greatly improved by the subsequent TAC film.

The disclosure of Japanese Patent Application No. 2012-261602 is incorporated herein by reference in its entirety. All documents, patent applications, and technical specifications described in this specification are incorporated by reference to the same extent as each of the documents, patent applications, and technical specifications.

1‧‧‧Triacetyl cellulose (TAC) film 1

2‧‧‧glass plate

3‧‧‧Triacetyl cellulose (TAC) film 3

Claims (14)

An adhesive comprising a condensate of a cellulose derivative and a polyoxyalkylene having a substituent selected from at least one selected from the group consisting of a hydroxyl group and an alkoxy group. An adhesive agent according to claim 1, wherein the polyoxyalkylene has an average value of a total number of substituents selected from at least one of a group consisting of a hydroxyl group and an alkoxy group. One germanium atom is 0.5 or more. The adhesive of claim 1, wherein the cellulose derivative comprises a structural unit derived from glucose, and the structural unit derived from glucose has at least one selected from the group consisting of an alkyl group and a thiol group. The substituent has an average value of the total number of the substituents of 1.0 or more per one structural unit derived from glucose. The adhesive agent of the first aspect of the patent application, further comprising an organic solvent comprising at least one selected from the group consisting of an ether solvent, a ketone solvent, and an ester solvent. A method for producing an adhesive, which comprises the adhesive of claim 1, comprising a cellulose derivative and a substituent having at least one selected from the group consisting of a hydroxyl group and an alkoxy group. The mixture of polyoxyalkylene is heated to obtain a condensate of the cellulose derivative and the polyoxyalkylene. The method for producing an adhesive according to claim 5, further comprising a solution containing a decane compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group, water, and an organic solvent. The decane compound is subjected to hydrolysis and polycondensation to obtain a polyoxyalkylene having a substituent selected from at least one selected from the group consisting of a hydroxyl group and an alkoxy group. The method for producing an adhesive according to claim 6, wherein the mass ratio of the decane compound to the cellulose derivative is 1:9 to 9:1. a method for producing an adhesive according to claim 6 wherein the decane is contained The solution of the compound, water and organic solvent further contains an acidic catalyst. A laminate comprising a first layer and a second layer containing at least one of the inorganic materials, using an adhesive as in the first aspect of the patent application or a manufacturing method using an adhesive as in the fifth aspect of the patent application The resulting adhesive is subjected to the resulting structure. The laminate according to claim 9, wherein one of the first layer and the second layer contains an inorganic material, and the other contains an organic material. The laminate according to claim 9, wherein the inorganic material comprises at least one selected from the group consisting of a metal and a metal oxide. The laminate according to claim 10, wherein the organic material comprises at least one selected from the group consisting of a cellulose resin, a polyimide resin, a polyamide resin, and a polyester resin. A method for producing a laminate according to claim 9, comprising the steps of: sequentially arranging the first layer, an adhesive layer containing the adhesive, and the second layer, and The first layer is followed by the second layer. The method for producing a laminate according to claim 13, wherein the step is carried out by applying at least one of heat and pressure.