JP2009079154A - Temperature responsive surface member and manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a temperature responsive surface member which can exhibit hydrophilic/hydrophobic change by temperature and is excellent in durability, particularly, in wear resistance, and a manufacturing method of temperature responsive surface member, capable of easily manufacturing a temperature responsive surface member excellent in durability which can maintain a hydrophilic/hydrophobic change effect by temperature. <P>SOLUTION: The temperature responsive surface member comprises a polymer layer including an amido group-containing polymer having a phase transfer temperature ranging from 20 to 50°C, the polymer layer being formed on a polymerization initiatable substrate, chemically bonded with the substrate, and derived from a compound containing an amido group and a polymerizable group in the molecule. As an amido group-containing monomer which constitutes the compound and can give temperature responsiveness to the generated polymer, N-isopropyl acrylamide is preferred. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a temperature-responsive surface member and a manufacturing method thereof. Specifically, a polymer layer comprising a polymer having a phase transition temperature in the range of 20 to 50 ° C., derived from a compound having a specific amide bond capable of imparting temperature responsiveness in which surface hydrophilicity / hydrophobicity changes greatly depending on temperature. And a method for manufacturing the same.

Poly N-isopropylacrylamide (PNIPAAm) is known as a temperature-responsive polymer whose physical properties change with changes in temperature. This PNIPAAm is a water-soluble compound at a temperature lower than 32 ° C., but rapidly dehydrates at a temperature higher than 32 ° C., and a polymer chain aggregates due to hydrophobic interaction to cause phase separation. The temperature at which this physical property change occurs is called the lower critical solution temperature (LCST) (see Non-Patent Document 1, for example). When such PNIPAAm is introduced into the substrate surface, the hydrophilicity / hydrophobicity of the surface is increased. Can be greatly changed by the temperature, that is, the contact angle of water on such a surface changes due to the structural change. For example, it is known that a film obtained by grafting NIPAAm on a silicon substrate by surface-initiated living radical polymerization exhibits a contact angle of water of 63 ° at 25 ° C. and 93 ° at 40 ° C. (for example, non-patent Reference 2). An example in which NIPAAm is grafted onto silica particles by living radical polymerization is also known (see, for example, Patent Document 1).
Such a temperature-responsive surface material is used as a drug carrier in a drug delivery system because of a rapid change in the balance between hydrophilicity and hydrophobicity (Non-Patent Document 3), protein adsorption / desorption membrane ( Non-patent document 4), use for chromatographic materials with varying affinity (non-patent document 5) and the like has been proposed.

As a method for immobilizing PNIPAAm on a substrate, a method called electron beam graft polymerization (for example, forming PNIPAAm on a substrate by contacting the substrate with N-isopropylacrylamide (NIPAAm) and irradiating an electron beam (for example, NIPAAm graft polymerization methods by surface-initiated living radical polymerization as described in Patent Document 2 and Patent Document 3) and Patent Document 1 are known. However, in the electron beam graft polymerization method, the formed PNIPAAm has poor durability (abrasion resistance), and the electron beam irradiation causes large damage to the inside of the substrate. There are problems such as the physical properties being damaged, and the use of an electron beam irradiation apparatus, which increases the cost of the apparatus.
On the other hand, in the surface-initiated living radical polymerization method, the substrate pretreatment process up to the polymerization process is complicated, and the polymerization time usually requires a long time of 1 to 20 hours, and the durability of the formed PNIPAAm ( The problem is that the (rubbing resistance) is not good.
Examples of the use of the temperature-responsive surface member whose surface hydrophilicity / hydrophobicity changes due to such a temperature change include a release material and a transfer material using releasability and transferability as described above. When it is used in the process, durability that does not change the physical properties of the surface even when operated multiple times, particularly durability against rubbing (rubbing resistance) is required, but a surface modification method that satisfies this has not yet been found. There is no current situation.
JP 2007-69193 A JP-A-2-21865 JP 2004-261532 A Prog. Polym. Sci. , 17, P163-249 (1992) Angew. Chem. Int. Ed. , 43, P357-360 (2004) J. et al. Controlled. Release, 59, P287 (1999) J. et al. Controlled. Release, 55, P121 (1998) Anal. Chem. , 6, P1125 (1999)

  An object of the present invention made in view of the above problems is to provide a temperature-responsive surface member that exhibits a change in hydrophilicity / hydrophobicity due to temperature and is excellent in durability, in particular, friction resistance. A further object of the present invention is to provide a method for producing a temperature-responsive surface member, which can easily produce a temperature-responsive surface member having excellent durability and having a hydrophilic / hydrophobic change effect depending on temperature. .

The present inventor can achieve the above object by providing a polymerization initiation layer having a crosslinked structure on a substrate and providing a polymer layer having a specific amide group capable of imparting temperature responsiveness on the surface thereof. The headline and the present invention were completed.
<1> On a substrate having a polymerization initiating ability, a phase transition in the range of 20 to 50 ° C. derived from a compound chemically bonded to the substrate having the initiating ability and having an amide group and a polymerizable group in the molecule. A temperature-responsive surface member comprising a polymer layer made of a polymer having temperature.
<2> The substrate having the polymerization initiating ability is a substrate having a polymerization initiating layer formed by including a crosslinkable polymerization initiator on the support surface, and the crosslinkable polymerization initiator starts thermal crosslinkable photoradical polymerization. The temperature-responsive surface according to <1>, wherein the polymerizable group in the compound containing an amide group and a polymerizable group in the molecule is a radical polymerizable double bond Element.
<3> The temperature-responsive surface member according to <1> or <2>, wherein the compound containing an amide group and a polymerizable group in the molecule is a polymer.
<4> The temperature-responsive surface member according to <3>, wherein the polymer containing an amide group and a polymerizable group in the molecule is an acrylic polymer.

<5> The temperature-responsive surface member according to any one of <1> to <4>, wherein the amide group is N-isopropylacrylamide.
<6> The temperature-responsive surface member according to any one of <2> to <5>, wherein the crosslinkable polymerization initiator is a polymer having a crosslinkable group and a polymerization initiating partial structure. .
<7> The temperature-responsive surface member according to <6>, wherein the crosslinkable polymerization initiator is a polymer having a benzophenone structure in the molecule.
<8> The temperature-responsive surface member according to any one of <1> to <7>, wherein the substrate is a resin film.
<9> The temperature-responsive surface member according to <8>, wherein the resin film is a resin film made of a polyester resin or a polyimide resin.
<10> (I) a step of bringing a compound having an amide group and a polymerizable group into contact with the surface of a substrate having polymerization initiating ability; and (II) applying energy to the entire surface or a specific region of the substrate. And a step of forming a polymer layer made of a polymer having an amide group in the energy imparting region and having a phase transition temperature in the range of 20 to 50 ° C., and a method for producing a temperature-responsive surface member.
<11> The substrate having the polymerization initiating ability is provided with a polymerization initiating layer coating liquid layer containing a crosslinkable polymerization initiator on a support, and thereafter, energy is applied to form a cross-linked structure, thereby supporting the surface of the support. The method for producing a temperature-responsive surface member according to <10>, which is obtained by forming a polymerization initiation layer on the surface.

  According to the present invention, a change in hydrophilicity / hydrophobicity due to temperature is manifested, and the durability, in particular, a temperature-responsive surface member excellent in friction resistance, and the durability / hydrophobicity change effect due to temperature persists. It is possible to provide a method for producing a temperature-responsive surface member that can easily produce a temperature-responsive surface member having excellent properties.

The present invention will be described in detail below.
The temperature-responsive surface member of the present invention is a compound that chemically binds to the base material on a substrate having polymerization initiating ability and contains an amide group and a polymerizable group in the molecule, and is derived from the compound. A compound capable of imparting a property having a phase transition temperature in the range of 20 to 50 ° C. to the polymer, that is, a polymer having an amide group and a polymerizable group in the molecule and having a phase transition temperature in the range of 20 to 50 ° C. And a polymer layer made of a polymer that has an amide group and has a phase transition temperature in the range of 20 to 50 ° C., preferably (I) A step of bringing a compound having an amide group and a polymerizable group into contact with the surface of the substrate having a polymerization initiating ability; and (II) applying energy to the entire surface or a specific region of the substrate, Has an amide group Forming a polymer layer comprising a polymer having a phase transition temperature in the range of 20 to 50 ° C., it can be obtained by a production method including.
Hereinafter, the structure of the temperature-responsive surface member of the present invention will be described in detail according to the production method.

[substrate]
First, the substrate used in the present invention will be described. Although the substrate in the present invention is required to have a polymerization initiating ability, a polymerization initiating layer containing a polymerization initiator is formed on an appropriate support surface even if the substrate itself is made of a material having a polymerization initiating ability. A thing may be used as a substrate.
The substrate support used in the present invention is preferably a dimensionally stable plate, such as paper, paper laminated with plastic (for example, polyethylene, polypropylene, polystyrene, etc.), metal plate, and the like. (For example, aluminum, zinc, copper, etc.), plastic film (for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl Acetal, polyimide, epoxy, bismaleimide resin, polyphenylene oxide, liquid crystal polymer, polytetrafluoroethylene, etc.), paper or plastic film laminated or vapor-deposited with the above metals, etc. It is included. As a base material used for this invention, a polyester resin or a polyimide resin is preferable.
In addition, when a compound having an amide group and a radical polymerizable double bond in the molecule as described above can be directly chemically bonded to these substrate supports, these substrate supports are used as they are. Used as a substrate in the invention.

When the substrate support is a resin film, the resin film that can be used in the present invention is not particularly limited as long as it is a film capable of holding a graft polymer, and can be appropriately selected according to the purpose of use.
Specifically, polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide resin, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, cellulose acylate resin , Polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified carbonate resin, alicyclic modified polycarbonate resin, acryloyl compound And a resin film formed of a resin selected from thermoplastic resins such as Of these resins for film formation, resins having a Tg of 120 ° C. or higher are preferred. Specific examples (numbers in parentheses indicate “glass transition temperature (Tg)”) are polyester resins, particularly polyethylene naphthalate. Resin (PEN: 121 ° C.), polyarylate resin (PAr: 210 ° C.), polyethersulfone resin (PES: 220 ° C.), fluorene ring-modified carbonate resin (BCF-PC: Example 4 of JP-A-2000-227603) Compound: 225 ° C.), alicyclic modified polycarbonate resin (IP-PC: compound of Example 5 of JP 2000-227603 A: 205 ° C.), acryloyl compound (Example 1 of JP 2002-80616 A) A film made of a compound such as:
The thickness of the resin film constituting such a substrate support is selected according to the purpose of use and is not particularly limited, but is generally about 10 μm to 1 mm.

In the present invention, a substrate formed by including a polyimide having a polymerization initiation site in the skeleton (hereinafter, appropriately referred to as a specific polyimide) as shown below can also be used. Since the resin film made of such a material itself has a polymerization initiating ability, it can be used as it is as a substrate in the present invention without forming a polymerization initiating layer described in detail below.
The substrate having the ability to initiate polymerization comprising this specific polyimide is prepared by preparing a polyimide precursor compound, molding the polyimide precursor compound into a desired substrate shape, and then performing heat treatment to start polymerization of the polyimide precursor. It can be produced by changing to a specific polyimide structure having a function.

  Although the specific example of the specific polyimide produced as mentioned above is shown, it is not limited to these.

In the above formula, n represents the number of polymerization of the notation structural unit, preferably 2 to 10000, more preferably 50 to 600.
A resin film having such a polymerization initiating ability can be used as it is as a substrate in the present invention, but when a resin film having no polymerization initiating ability exemplified in the substrate support is used as a support, A polymerization initiation layer to be described later is formed on the surface to form a substrate.

[Polymerization initiation layer]
The polymerization initiation layer is preferably a layer containing a polymer compound and a polymerization initiator, or a layer containing a polymerizable compound and a polymerization initiator.
The polymerization initiating layer in the present invention can be formed by dissolving a necessary component in a solvent capable of dissolving, providing a coating layer on the substrate surface by a method such as coating, and hardening by heating or light irradiation. .

  The compound used for the polymerization initiation layer in the present invention can be used without particular limitation as long as it has good adhesion to the substrate and generates active species by energy application such as irradiation with actinic rays. . Specific examples include a mixture of a polyfunctional monomer or a hydrophobic polymer having a polymerizable group in the molecule and a polymerization initiator.

Specific examples of the hydrophobic polymer having a polymerizable group in the molecule include diene homopolymers such as polybutadiene, polyisoprene and polypentadiene, allyl (meth) acrylate, 2-allyloxyethyl. Homopolymers of allyl group-containing monomers such as methacrylic soot; styrene, (meth) acrylic acid esters, (meth) acrylonitrile containing diene monomers such as butadiene, isoprene and pentadiene or allyl group-containing monomers as constituent units Binary or multi-component copolymers such as: unsaturated polyester, unsaturated polyepoxide, unsaturated polyamide, unsaturated polyacryl, linear polymer having a carbon-carbon double bond in the molecule, such as high-density polyethylene, or three-dimensional Macromolecules; and the like.
In this specification, when referring to both or one of “acrylic and methacrylic”, it may be expressed as “(meth) acrylic”.
The content of these polymerizable compounds is preferably in the range of 10 to 95% by mass and particularly preferably in the range of 10 to 80% by mass in the polymerization start layer.

The polymerization initiation layer contains a polymerization initiator for expressing polymerization initiation ability by applying energy. The polymerization initiator used here is a known thermal polymerization initiator, photopolymerization initiator, etc. that can exhibit polymerization initiation ability by predetermined energy, for example, irradiation with actinic rays, heating, irradiation with electron beam, etc. Depending on the purpose, it can be appropriately selected and used. Among these, use of photopolymerization is preferable from the viewpoint of production suitability, and therefore, a photopolymerization initiator is preferably used.
The photopolymerization initiator is not particularly limited as long as it is active with respect to irradiated actinic rays and can be subjected to surface graft polymerization from the polymerization initiation layer containing the photopolymerization initiator, and examples thereof include radical polymerization initiators and anionic polymerizations. An initiator, a cationic polymerization initiator, and the like can be used, but a radical polymerization initiator is preferable from the viewpoint of reactivity.

Specific examples of such a photopolymerization initiator include p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one. Acetophenones such as: benzophenone (4,4′-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, ketones; benzoin, benzoin methyl ether, benzoin isopropyl Examples thereof include benzoin ethers such as ether and benzoin isobutyl ether; benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone, and the like.
The content of the polymerization initiator is preferably in the range of 0.1 to 70% by mass, particularly preferably in the range of 1 to 40% by mass in terms of solid content in the polymerization initiator layer.

  In addition, the polymerization initiator itself may be a polymer, and examples thereof include compounds composed of structural units represented by the following (1) to (15). These compounds are disclosed in JP-A-9-77891, JP-A-10-45927, Japanese Patent Application No. 2006-053430, Japanese Patent Application No. 2006-264706, Photochemistry & Photobiology, Vol. 5, p46 (1999), etc., and is a polymer radical photopolymerization initiator having an active carbonyl group, trichloromethyltriazine, and thioxanthone in the side chain.

  The weight average molecular weight of the polymer type photoradical polymerization initiator is preferably 10,000 or more, and more preferably 30,000 or more. The upper limit of the weight average molecular weight is preferably 100,000 from the viewpoint of solubility. The polymerization number n of each structural unit can be appropriately determined so that the molecular weight falls within the above range. Here, in (15), x and y represent mole fractions, and x + y = 100 (x ≠ 0, y ≠ 0).

The solvent used when applying the polymerizable compound and the polymerization initiator is not particularly limited as long as these components can be dissolved. From the viewpoint of easy drying and workability, a solvent having a boiling point that is not too high is preferable. Specifically, a solvent having a boiling point of about 40 ° C to 150 ° C may be selected.
Specifically, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, methanol, Ethanol, 1-methoxy-2-propanol, 3-methoxypropanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, - such as methoxypropyl acetate.
These solvents can be used alone or in combination. The concentration of the solid content in the coating solution is suitably 2 to 50% by mass.

The coating amount when forming the polymerization initiating layer on the substrate is 0.1 in terms of the mass after drying, from the viewpoint of sufficient polymerization initiating ability and maintaining film properties to prevent film peeling. -20 g / m ² is preferable, and 0.5-15 g / m ² is more preferable.

In the present invention, as described above, the composition for forming the polymerization initiation layer is disposed on the substrate by coating or the like, and the film is formed by removing the solvent to form the polymerization initiation layer. The film is preferably hardened by heating and / or light irradiation. In particular, if the film is dried by heating and then preliminarily cured by light irradiation, the polymerizable compound is cured to some extent in advance, so that after the polymerization polymer is formed on the polymerization initiation layer, the polymerization initiation layer is removed. This is preferable because it is possible to effectively suppress such a situation.
The heating temperature and time may be selected under conditions that allow the coating solvent to be sufficiently dried. However, from the viewpoint of production suitability, the temperature is 100 ° C. or less, the drying time is preferably within 30 minutes, and the drying temperature is 40 to 80 ° C. It is more preferable to select heating conditions within a drying time of 10 minutes.

  The light irradiation performed as desired after heat-drying can use the light source used for the production | generation reaction of the graft polymer mentioned later. In the subsequent graft polymer generation step, the polymerization initiator existing in the polymerization start layer cures the polymerizable compound from the viewpoint of not inhibiting the active point of the polymerization start layer generated by energy application and the generation of the graft polymer. Even when radical polymerization is performed, it is preferable to irradiate with light so that it is not completely consumed. About light irradiation time, although it changes with the intensity | strength of a light source, generally it is preferable within 30 minutes. As a standard for such pre-curing, it can be mentioned that the film remaining rate after solvent cleaning is 80% or less and the initiator remaining rate after pre-curing is 1% or more.

In addition to the polymerization initiation layer containing the polymerizable compound and the polymerization initiator, a polymerization initiation layer using a polymer in which a polymerization initiation group described in JP-A-2004-161995 is pendant on a side chain is more preferable. . Specifically, this polymer is a polymer having a functional group (polymerization initiating group) having a polymerization initiating ability in the side chain and a crosslinkable group (hereinafter referred to as a specific polymerization initiating polymer). A polymerization initiating layer having a polymerization initiating group bonded to a chain and in which the polymer chain is immobilized by a crosslinking reaction can be formed.
The polymerization initiating layer thus formed is most suitable as the polymerization initiating layer of the present application.

  Examples of the specific polymerization initiating polymer used here include polymers having a hydroxyl group, an amino group, and a carboxyl group as the crosslinkable groups described in paragraphs [0011] to [0158] of JP-A No. 2004-161995. Specific examples of particularly preferred specific polymerization initiating polymers include polymers containing the structural units shown below in the molar fractions shown below. Preferred molecular weights of these polymers are the same as those described above.

Furthermore, a polymer (specific polymerization initiating polymer) having an epoxy group as a crosslinkable group together with a partial structure having a polymerization initiating ability can also be mentioned as a preferred example. Examples of such compounds include (16) to (16) to Specific examples include compounds composed of the structural unit represented by (30).
Here, in (16) to (30), x and y represent mole fractions, and x + y = 100 (x ≠ 0, y ≠ 0).

  Furthermore, a polymer having a oxime ester group as a polymerization initiating group (specific polymerization initiating polymer) can also be mentioned as a preferred example, and as such a compound, structural units represented by (31) to (40) shown below Can be specifically mentioned.

-Formation of polymerization initiation layer-
When forming a polymerization initiating layer using such a specific polymerization initiating polymer containing a partial structure having a polymerization initiating ability, dissolve the above-mentioned specific polymerization initiating polymer in an appropriate solvent to prepare a coating solution, The coating solution is disposed on the substrate by coating or the like, and the solvent is removed to form a film. During this film formation, the crosslinking reaction proceeds. That is, the specific polymerization initiating polymer is immobilized by the progress of the crosslinking reaction. The immobilization by the crosslinking reaction includes a method using a self-condensation reaction of a specific polymerization initiating polymer and a method using a crosslinking agent in combination, and it is preferable to use a crosslinking agent. The crosslinking agent is also preferably added when the polymerization initiating layer is formed from a polymerizable compound (low molecular weight compound).
As a method of using the self-condensation reaction of the specific polymerization initiating polymer, for example, when the crosslinkable group is —NCO, an epoxy group or an alkoxysilyl group, self-condensation is performed by applying heat in the presence of a reaction catalyst as necessary. This utilizes the nature of the reaction. As this self-condensation reaction proceeds, a crosslinked structure can be formed.

When the polymerization initiating layer is formed, when a method of using a crosslinking agent in combination is employed, as the crosslinking agent used, a conventionally known one as described in Shinji Yamashita “Crosslinking agent handbook” can be used. .
Preferred combinations of the crosslinkable group and the crosslinker in the specific polymerization initiating polymer include (crosslinkable group, crosslinker) = (— COOH, polyvalent amine), (—COOH, polyvalent aziridine), (—COOH, Polyvalent isocyanate), (—COOH, polyvalent epoxy), (—NH ₂ , polyvalent isocyanate), (—NH ₂ , aldehydes), (—NCO, polyvalent amine), (—NCO, polyvalent isocyanate) , (—NCO, polyhydric alcohol), (—NCO, polyhydric epoxy), (—OH, polyvalent isocyanate), (—OH, polyvalent halogenated compound), (—OH, polyvalent amine), (− OH, polyhydric acid anhydride), (epoxy, polyhydric amine), (epoxy, polyhydric phenolic OH), (epoxy, polyhydric isocyanate), (epoxy, polycarboxylic acid), (epoxy, polyhydric acid) anhydrous Product), (epoxy, polyvalent epoxy), (alkoxysilyl, alkoxysilyl). Among these, (functional group, cross-linking agent) = (— OH, polyvalent isocyanate) is a more preferable combination in that a urethane bond is formed after the cross-linking and a high-strength cross-linking can be formed.

  Specific examples of the crosslinking agent that can be suitably used in the present invention include those having the following structures.

  Such a crosslinking agent is added to the coating solution containing the above-mentioned specific polymerization initiating polymer when the polymerization initiating layer is formed. Thereafter, the crosslinking reaction proceeds by the heat during the drying of the coating film, and a strong crosslinked structure can be formed. More specifically, the following ex1. Or the dehydration reaction indicated by ex2. The cross-linking reaction proceeds by the addition reaction represented by the above, and a cross-linked structure is formed. The temperature conditions in these reactions are preferably 50 ° C. or higher and 300 ° C. or lower, more preferably 80 ° C. or higher and 200 ° C. or lower.

  The amount of the crosslinking agent added in the coating solution varies depending on the amount of the crosslinkable group introduced into the specific polymerization initiating polymer, but the degree of crosslinking and the polymerization reaction due to the remaining unreacted crosslinking component remain. From the viewpoint of influence, it is usually preferably 0.01 to 50 equivalents, more preferably 0.01 to 10 equivalents, and 0.5 to 3 equivalents relative to the number of moles of the crosslinkable group. Is more preferable.

Moreover, the solvent used when apply | coating a polymerization start layer will not be restrict | limited especially if the above-mentioned specific polymerization start polymer melt | dissolves. From the viewpoint of easy drying and workability, a solvent having a boiling point that is not too high is preferable. Specifically, a solvent having a boiling point of about 40 ° C to 150 ° C may be selected.
Specifically, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, methanol, Ethanol, 1-methoxy-2-propanol, 3-methoxypropanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, - such as methoxypropyl acetate.
These solvents can be used alone or in combination. The solid content in the coating solution is suitably 2 to 50% by weight.

The coating amount of the polymerization initiating layer using the specific polymerization initiating polymer is preferably 0.1 to 20 g / m ² in terms of weight after drying, from the viewpoint of the ability to initiate surface graft polymerization and film properties, and more preferably 1 ~ 1
5 g / m ² is preferred.

[Polymer layer forming step]
In the present invention, in the case of a substrate surface having polymerization initiating ability, that is, in the case of a substrate having initiating ability, when the polymerization initiating layer is formed on the surface of the substrate itself or the substrate support surface, the polymerization initiating layer A polymer layer made of a polymer having at least one end directly chemically bonded to the surface of the substrate is formed. Here, a polymer comprising a polymer having an amide group and a phase transition temperature in the range of 20 to 50 ° C. by directly chemically bonding a compound containing an amide group and a polymerizable group in the molecule on the substrate. A layer is formed. The compound containing an amide group and a polymerizable group in the molecule used for forming such a polymer layer may be a monomer or an oligomer, and a polymer having an amide group and a polymerizable group in the molecule ( Polymerizable polymer).
In the present invention, on a substrate, a specific compound containing an amide group and a polymerizable group in the molecule is chemically bonded to form a polymer having at least one terminal bonded on the substrate. A means called surface graft polymerization is used. The polymerizable group is preferably a radical polymerizable double bond from the viewpoint of reactivity. The polymer formed by fixing one end on the substrate surface in this manner is hereinafter appropriately referred to as a surface graft polymer.

[Formation of surface graft polymer]
In general, graft polymerization is a method of synthesizing a graft (grafting) polymer by providing an active species on a polymer compound chain and further polymerizing a compound that initiates polymerization. Especially, when the polymer compound which gives active species forms a solid surface, it is called surface graft polymerization.

Any known method described in the literature can be used as the surface graft polymerization method applied to the present invention. For example, New Polymer Experimental Science 10, edited by Polymer Society, 1994, published by Kyoritsu Shuppan Co., Ltd., p135 describes a photograft polymerization method and a plasma irradiation graft polymerization method as surface graft polymerization methods. In addition, the adsorption technique manual, NTS Co., Ltd., supervised by Takeuchi, 1999.2, p203, p695 describes radiation-induced graft polymerization methods such as γ rays and electron beams.
As a specific method of the photograft polymerization method, the methods described in JP-A-63-92658, JP-A-10-296895, and JP-A-11-119413 can be used. From the viewpoint of producing more surface graft polymer, photograft polymerization is preferred, and UV light is preferably used because it can be formed with a simple apparatus.

In the present invention, as a means for directly chemically bonding a compound containing an amide group and a polymerizable group in the molecule to the substrate surface, specifically, an amide group and a polymerizable group are formed in the molecule on the substrate. A method is used in which energy is imparted to the substrate surface after contacting the compound having the active compound to generate active species (for example, radicals) and react with a polymerizable group with the active species on the substrate surface.
As described above, the surface graft polymerization reaction is caused between the active species on the substrate surface and the polymerizable group, so that in the present invention, the surface graft formed by using a compound having an amide group and a polymerizable group in the molecule. A polymer layer is formed from the polymer.

Next, a compound containing an amide group and a polymerizable group in the molecule will be described. This compound is a compound that can form a polymer having a phase transition temperature in the range of 20 to 50 ° C., and is characterized by containing an amide group and a polymerizable group in the molecule.
Examples of the polymerizable group in such a compound include a polymerizable group that polymerizes with an acid (cation) such as a vinyl ether group, an oxirane group, and an oxetane group, and a double bond that polymerizes with a radical such as a (meth) acryl group. From the viewpoint of reactivity, a radical polymerizable double bond is preferred.

The compound containing an amide group and a polymerizable group in the molecule has a specific amide group, and the polymer produced using the compound containing the specific amide group has a temperature of 20 to 50 ° C. It has a phase transition temperature in the range, and has physical properties that change hydrophilicity / hydrophobicity at the phase transition temperature. Preferred examples of the compound containing a specific amide group include compounds containing an amide group having a CON structure.
Examples of the compound having an amide group and a radical polymerizable double bond in the molecule include N- (or N, N-di) alkyl-substituted (meth) acrylamide derivatives. Specific examples include the following compounds. Here, the temperature indicated in parentheses attached to the compound includes an amide group as a partial structure capable of imparting temperature responsiveness to such a produced polymer, and has a phase in the range of 20 to 50 ° C. This is a phase transition temperature of a polymer derived from a compound capable of forming a polymer having a transition temperature, and the generated polymer causes a change in physical properties of hydrophilic (water-soluble) / hydrophobic with this temperature as a boundary. .

Specific examples of a compound having an amide group and a radical polymerizable double bond in the molecule capable of producing a polymer having a phase transition temperature in the range of 20 to 50 ° C., and a phase transition of the polymer produced from the compound Although temperature is mentioned, this invention is not restrict | limited to these.
N-n-propylacrylamide (21 ° C), N-isopropylacrylamide (32 ° C), Nn-propylmethacrylamide (27 ° C), N-isopropylmethacrylamide (43 ° C), N-cyclopropylacrylamide (45 ° C) ), N-ethoxyethylacrylamide (about 35 ° C.), N-ethoxyethyl methacrylamide (about 45 ° C.), N, N-diethylacrylamide (32 ° C.) and the like.
Among these, Nn-propylacrylamide, Nn-propylmethacrylamide, N-, which exhibits a phase transition temperature near room temperature and can produce a polymer capable of controlling the substrate surface properties by temperature control such as heating or cooling. Isopropylacrylamide, N-ethoxyethylacrylamide, and N, N-diethylacrylamide are easy to use as functional materials. In particular, N-isopropylacrylamide having a phase transition temperature of 32 ° C. is most preferable from the viewpoint of good balance between hydrophilicity and hydrophobicity.

The compound having an amide group and a radical polymerizable double bond in the molecule that can be a material for forming the surface graft polymer by the surface graft polymerization method is a polymer as shown below, even if it is a monomer or oligomer. Also good. It is possible to form a polymer layer in which the number of specific amide groups introduced in the molecule and the polymer chain length are controlled by chemically bonding a polymer compound with a predetermined molecular weight to the substrate surface to form a polymer layer. it can.
[Polymer having specific amide group and radical polymerizable double bond in molecule]
In the present invention, the polymer having an amide group and a radical polymerizable double bond in the molecule is obtained by using at least one monomer having a specific amide group that can impart temperature responsiveness to the polymer. A polymer in which a polymerizable group is introduced is used.
Examples of the polymerizable group to be introduced include ethylene addition polymerizable unsaturated groups such as a vinyl group, an allyl group, and a (meth) acryl group.

Hereinafter, a polymer having an amide group and a radical polymerizable double bond in the molecule will be described.
That is, the polymer having an amide group and a radical polymerizable double bond in the molecule used in the present invention is represented by the unit represented by the following general formula (1) and the following general formula (2). It is characterized by including a unit.

In general formula (1) and general formula (2), R ^{1 to} R ⁷ each independently represents a hydrogen atom or an alkyl group, and Y represents a single bond, —NR—, an oxygen atom, or a divalent organic compound. Represents a group, an ester group, an amide group or an ether group, wherein R represents a hydrogen atom or an alkyl group. Z represents a single bond, a divalent organic group, an ester group, an amide group, or an ether group, and L ¹ represents a divalent organic group. However, R ⁶ and R ⁷ do not represent a hydrogen atom at the same time.
Here, the alkyl group and the divalent organic group may further have a substituent, and examples of the substituent that can be introduced into the alkyl group include a phenyl group, a halogen atom, an alkoxy group, a cyano group, and a hydroxyl group. , Carboxyl group, amino group, ether group, ester group, acyl group, amide group, urethane group, urea group, etc., and the same substituent may be mentioned as a substituent that can be introduced into a divalent organic group. Can do.

In the general formula (1) and the general formula (2), when R ^{1 to} R ⁷ are substituted or unsubstituted alkyl groups, the unsubstituted alkyl group may be a methyl group, an ethyl group, or an n-propyl group. , Isopropyl group, n-butyl group, t-butyl group, and the substituted alkyl group is a methyl group, ethyl group, propyl group, butyl group substituted with methoxy group, chlorine, bromine, fluorine, etc. Is mentioned.
R ¹ is preferably a hydrogen atom or a methyl group.
R ² is preferably a hydrogen atom or a methyl group.
R ³ is preferably a hydrogen atom.
R ⁴ is preferably a hydrogen atom.
R ⁵ is preferably a hydrogen atom or a methyl group.
As a combination of (R ⁶ , R ⁷ ) in the general formula (2), (hydrogen atom, isopropyl group) is preferable.

When Y and Z are substituted or unsubstituted divalent organic groups, examples of the organic group of the divalent organic group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
As the aliphatic hydrocarbon group, a methylene group, an ethylene group, a propylene group, a butylene group, or a group in which these groups are substituted with a methoxy group, a hydroxy group, chlorine, bromine, fluorine, or the like is preferable.
As the aromatic hydrocarbon group, an unsubstituted phenyl group or a phenyl group substituted with a methoxy group, a hydroxy group, chlorine, bromine, fluorine, or the like is preferable.
Among _{them, - (CH 2) n -} (n is an integer of 1 to 3) are preferred, more preferably -CH ₂ -.

L ¹ is preferably a divalent organic group having a urethane bond or a urea bond, and among them, those having a total carbon number of 1 to 9 are preferable.
More specifically, the structure of L ¹ is preferably a structure represented by the following formula (1-1).

In the above formula (1-1), R ^a and R ^b each independently represent a substituted or unsubstituted methylene group, ethylene group, propylene group, butylene group.

  In the amide group-containing polymerizable polymer according to the present invention, the unit represented by the general formula (1) is preferably a unit represented by the following general formula (3).

In the general formula (3), R ¹ , R ² , Z, and L ¹ have the same meanings as in the general formula (1), and preferred examples are also the same. W represents -NR- or an oxygen atom, and R represents a hydrogen atom or an alkyl group.

  A polymer that contains an amide group and a polymerizable group in a molecule that can be used in the present invention, and that can form a polymer having a phase transition temperature in the range of 20 to 50 ° C. (hereinafter, appropriately referred to as an amide group-containing polymerizable polymer). ), The unit represented by the general formula (3) is preferably a unit represented by the following general formula (4).

In General Formula (4), R ¹ , R ² , and L ¹ have the same meanings as in General Formula (1). V and W each independently represent —NR— or an oxygen atom, and R represents a hydrogen atom or an alkyl group.

Here, it is a preferred embodiment that W in the general formula (4) is an oxygen atom.
Further, it is preferable that the L ¹ in the general formula (4) is a divalent organic group having a urethane bond or a urea bond.
Furthermore, it is more preferable that L ¹ in the general formula (4) is a divalent organic group having 1 to 9 carbon atoms in total.

In Formula (3) and Formula (4), W is preferably an oxygen atom.
In Formulas (3) and (4), L ¹ is preferably a divalent organic group having a urethane bond or a urea bond, and among them, those having 1 to 9 carbon atoms are particularly preferable.

The amide group-containing polymerizable polymer according to the present invention includes a unit represented by the above formulas (1) to (4), and has a polymer group and an amide group in the side chain. It is.
This amide group-containing polymerizable polymer can be synthesized, for example, as follows.

As the type of polymerization reaction, radical polymerization, cationic polymerization, and anionic polymerization are known, but radical polymerization and cationic polymerization are preferably used from the viewpoint of reaction control.
The nitrile group-containing polymerizable polymer of the present invention includes: 1) the case where the polymerization form forming the polymer main chain is different from the polymerization form of the polymerizable group introduced into the side chain, and 2) the polymerization form forming the polymer main chain. And the synthesis method of the polymerizable group introduced into the side chain is different in the synthesis method.

1) When the polymerization form forming the polymer main chain is different from the polymerization form of the polymerizable group introduced into the side chain When the polymerization form forming the polymer main chain is different from the polymerization form of the polymerizable group introduced into the side chain The polymer main chain formation is performed by radical polymerization, and there is an embodiment in which the polymerization form of the polymerizable group introduced into the side chain is cationic polymerization.

  Examples of the monomer used in the embodiment in which the polymer main chain is formed by radical polymerization and the polymerization form of the polymerizable group introduced into the side chain is cationic polymerization include the following compounds.

-Monomers used to form polymerizable group-containing units As monomers used to form polymerizable group-containing units used in this embodiment, vinyl (meth) acrylate, allyl (meth) acrylate, 4- ( (Meth) acryloylbutane vinyl ether, 2- (meth) acryloylethane vinyl ether, 3- (meth) acryloylpropane vinyl ether, (meth) acryloyloxydiethylene glycol vinyl ether, (meth) acryloyloxytriethylene glycol vinyl ether, (meth) acryloyl 1st ter Pioneer, 1- (meth) acryloyloxy-2-methyl-2-propene, 1- (meth) acryloyloxy-3-methyl-3-butene, 3-methylene-2- (meth) acryloyloxy-norbornane, 4,4′-ethylidene diphenol di (meth) acrylate, methacrolein di (meth) acryloyl acetal, p-((meth) acryloylmethyl) styrene, allyl (meth) acrylate, 2- (bromomethyl) vinyl acrylate, 2- (Hydroxymethyl) allyl acrylate and the like.

Monomers used to form amide group-containing units Monomers used to form amide group-containing units used in this embodiment include N-methylacrylamide, N-ethylacrylamide, Nn-propylacrylamide, N- Examples thereof include isopropylacrylamide, Nn-butylacrylamide, Nt-butylacrylamide, and methacryl derivatives thereof.
A monomer having a structure in which a part of hydrogen of the monomer is substituted with an alkoxy group, a halogen, a cyano group, or the like can also be used.

Polymerization methods include general radical polymerization methods described in Experimental Chemistry Course “Polymer Chemistry” Chapter 2-2 (p34) and “Experimental Methods for Polymer Synthesis” written by Takayuki Otsu Chapter 5 (p125). Can be used. As the initiator for radical polymerization, a high-temperature initiator that requires heating at 100 ° C. or higher, a normal initiator that starts by heating at 40 to 100 ° C., a redox initiator that starts at a very low temperature, and the like are known. In general, an initiator is preferred from the viewpoint of stability of the initiator and ease of handling of the polymerization reaction.
Usual initiators include benzoyl peroxide, lauroyl peroxide, peroxodisulfate, azobisisobutyronitrile, azovir-2,4-dimethylvaleronitrile.

2) When the polymerization form forming the polymer main chain is the same as the polymerization form of the polymerizable group introduced into the side chain Polymerization form forming the polymer main chain and the polymerization form of the polymerizable group introduced into the side chain Are the same, there is an embodiment in which both are radical polymerization.

  In an embodiment in which both are radical polymerization, the synthesis methods include i) a method of copolymerizing a monomer having an amide group and a monomer having a polymerizable group, and ii) a monomer having an amide group and a double bond precursor. A method in which a monomer is copolymerized and then a double bond is introduced by treatment with a base or the like; iii) a polymer having an amide group is reacted with a monomer having a polymerizable group to introduce a double bond (polymerizable group) Method). From the viewpoint of synthesis suitability, ii) a method in which a monomer having an amide group and a monomer having a double bond precursor are copolymerized and then a double bond is introduced by treatment with a base or the like, iii) an amide In this method, a polymer having a group and a monomer having a polymerizable group are reacted to introduce a polymerizable group.

  Examples of the monomer having a polymerizable group used in the synthesis method i) include allyl alcohol and the following compounds.

  Examples of the monomer having a double bond precursor used in the synthesis method ii) include compounds represented by the following formula (a).

In the above formula (a), A is an organic atomic group having a polymerizable group, R ^{1 to} R ³ are each independently a hydrogen atom or a monovalent organic group, and B and C are removed by elimination reaction. It is a leaving group, and the elimination reaction here means that C is extracted by the action of a base and B is eliminated. B is preferably eliminated as an anion and C as a cation.
Specific examples of the compound represented by the formula (a) include the following compounds.

  Further, in the synthesis method of ii), in order to convert the double bond precursor to a double bond, as shown below, a method of removing leaving groups represented by B and C by an elimination reaction, That is, a reaction in which C is extracted by the action of a base and B is eliminated is used.

  Preferred examples of the base used in the elimination reaction include alkali metal hydrides, hydroxides or carbonates, organic amino compounds, and metal alkoxide compounds. Preferred examples of alkali metal hydrides, hydroxides or carbonates include sodium hydride, calcium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, sodium carbonate, Examples include potassium hydrogen carbonate and sodium hydrogen carbonate. Preferable examples of the organic amine compound include trimethylamine, triethylamine, diethylmethylamine, tributylamine, triisobutylamine, trihexylamine, trioctylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N- Methyldicyclohexylamine, N-ethyldicyclohexylamine, pyrrolidine, 1-methylpyrrolidine, 2,5-dimethylpyrrolidine, piperidine, 1-methylpiperidine, 2,2,6,6-tetramethylpiperidine, piperazine, 1,4-dimethyl Piperazine, quinuclidine, 1,4-diazabicyclo [2,2,2] -octane, hexamethylenetetramine, morpholine, 4-methylmorpholine, pyridine, picoline, 4-dimethylaminopyridine, Cytidine, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), N, N'-dicyclohexylcarbodiimide (DCC), diisopropylethylamine, Schiff base, and the like. Preferable examples of the metal alkoxide compound include sodium methoxide, sodium ethoxide, potassium t-butoxide and the like. These bases may be used alone or in combination of two or more.

  Examples of the solvent used for adding (adding) the base in the elimination reaction include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate , Ethyl lactate, water and the like. These solvents may be used alone or in combination of two or more.

  The amount of the base used may be equal to or less than the equivalent to the amount of the specific functional group (the leaving group represented by B or C) in the compound, or may be equal to or more than the equivalent. Moreover, when an excess base is used, it is also a preferred form to add an acid or the like for the purpose of removing the excess base after the elimination reaction.

In the synthesis method of iii), the monomer having a polymerizable group to be reacted with a polymer having an amide group varies depending on the type of the reactive group in the polymer having an amide group, but has the following combinations of functional groups: Can be used.
That is, (polymer reactive group, monomer functional group) = (carboxyl group, carboxyl group), (carboxyl group, epoxy group), (carboxyl group, isocyanate group), (hydroxyl group, carboxyl group), (hydroxyl group, epoxy) Group), (hydroxyl group, isocyanate group) and the like.
Specifically, the following monomers can be used.

The ratio of the polymerizable group-containing unit and the amide group-containing unit of the amide group-containing polymerizable polymer according to the present invention synthesized as described above is preferably in the following range with respect to the entire copolymerization component.
That is, it is preferable that a polymeric group containing unit is contained with 5-50 mol% with respect to the whole copolymerization component, More preferably, it is 5-40 mol%. If it is 5 mol% or less, the reactivity (curability and polymerizability) is lowered, and if it is 50 mol% or more, it is easily gelled during synthesis and is difficult to synthesize.
Moreover, it is preferable that an amide group containing unit is contained by 10-95 mol% with respect to the whole copolymerization component, More preferably, it is 20-95 mol%. When the amount is 10 mol% or less, the obtained polymer does not exhibit sufficient temperature response.

In addition, the amide group-containing polymerizable polymer according to the present invention may contain other units in addition to the amide group-containing unit and the polymerizable group-containing unit. As the monomer used to form the other unit, any monomer can be used as long as it does not impair the effects of the present invention.
Specifically, when the polymer main chain is formed by radical polymerization, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl Unsubstituted (meth) acrylates such as (meth) acrylate and stearyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 3,3,3-trifluoropropyl (meth) acrylate, Halogen-substituted (meth) acrylic esters such as 2-chloroethyl (meth) acrylate, ammonium group-substituted (meth) acrylic esters such as 2- (meth) acryloyloxyethyltrimethylammonium chloride, butyl (meth) acrylamide, Iso (Meth) acrylamides such as propyl (meth) acrylamide, octyl (meth) acrylamide, dimethyl (meth) acrylamide, styrenes such as styrene, vinylbenzoic acid, p-vinylbenzylammonium chloride, N-vinylcarbazole, vinyl acetate, Vinyl compounds such as N-vinylacetamide and N-vinylcaprolactam, and dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-ethylthio-ethyl (meth) acrylate, (meth) acrylic acid, 2 -Hydroxyethyl (meth) acrylate etc. can be used.
Moreover, the macromonomer obtained using the monomer of the said description can also be used.

  The weight average molecular weight (Mw) of the amide group-containing polymerizable polymer according to the present invention is preferably 3000 to 200,000, more preferably 4000 to 100,000.

Specific examples of the amide group-containing polymerizable polymer used in the present invention are shown below. However, the copolymer which can be used in the present invention is not limited to these.
In addition, the weight average molecular weights of these specific examples are all in the range of 10,000 to 60000.

<Usage>
The amide group-containing polymerizable polymer according to the present invention can be mixed with other components (for example, a solvent) and used as a composition. In that case, as content in the composition of the amide group containing polymeric polymer of this invention, the range of 2 mass%-50 mass% is preferable, and the range of 5 mass%-20 mass% is more preferable.

The solvent used in the composition containing the amide group-containing polymerizable polymer according to the present invention is not particularly limited as long as the polymer can be dissolved. Further, a surfactant may be further added to the solvent.
Examples of the solvent that can be used include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin, propylene glycol monomethyl ether, acids such as acetic acid, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, formamide, dimethylacetamide, Examples thereof include amide solvents such as N-methylpyrrolidone, nitrile solvents such as acetonitrile and propylonitrile, and ester solvents such as methyl acetate and ethyl acetate.
Of these, amide, ketone, and nitrile solvents are preferable, and ketone and nitrile solvents are more preferable. Specifically, acetone, dimethylacetamide, methyl ethyl ketone, cyclohexanone, acetonitrile, and propionitrile are preferable.
Moreover, when using the composition containing the amide group containing polymeric polymer of this invention as a coating liquid, it is preferable to use the solvent whose boiling point is 50-150 degreeC from handling ease.
In addition, these solvents may be used alone or in combination.

  The surfactant that can be added to the composition as necessary may be any that dissolves in the solvent. Examples of such a surfactant include an anionic interface such as sodium n-dodecylbenzenesulfonate. Activators, cationic surfactants such as n-dodecyltrimethylammonium chloride, polyoxyethylene nonylphenol ether (commercially available products include, for example, Emulgen 910, manufactured by Kao Corporation), polyoxyethylene sorbitan monolaurate ( Examples of commercially available products include non-ionic surfactants such as trade name “Tween 20” and polyoxyethylene lauryl ether.

  Moreover, a plasticizer can also be added to the said composition as needed. Usable plasticizers include general plasticizers such as phthalates (dimethyl ester, diethyl ester, dibutyl ester, di-2-ethylhexyl ester, dinormal octyl ester, diisononyl ester, dinonyl ester, diisodecyl ester). Ester, butyl benzyl ester), adipic acid ester (dioctyl ester, diisononyl ester), azelain san dioctyl, sebacin sun ester (dibutyl ester, dioctyl ester) tricresyl phosphate, acetyl citrate tributyl, epoxidized soybean oil, trimellit High boiling solvents such as trioctyl acid, chlorinated paraffin, dimethylacetamide, and N-methylpyrrolidone can also be used.

[Energy provision]
As a method of imparting energy when these specific amide compounds containing an amide group and a polymerizable group in the molecule are chemically bonded to a substrate having a polymerization initiating ability, for example, a polymerization initiating layer provided on a substrate support. Depending on the polymerization initiation part (site), for example, radiation irradiation such as heating or exposure can be used. For example, light irradiation with a UV lamp, visible light, or the like, heating with a hot plate, or the like is possible. Examples of the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Moreover, g line and i line are also used. The time required for applying energy is usually 10 seconds to 10 minutes, although it varies depending on the amount of the target graft polymer produced and the light source. When this energy application is performed over the entire required region of the substrate, a polymer layer is formed over the entire substrate surface, and a patterned polymer layer is formed by applying pattern energy.

Through the above-described steps, surface graft polymerization can produce a surface graft polymer having an amide group on the substrate and a phase transition temperature in the range of 20 to 50 ° C., and forming a polymer layer composed of the polymer. The temperature responsive surface member of the present invention can be obtained.
The thus-obtained temperature-responsive surface member of the present invention changes its surface hydrophilicity / hydrophobicity with changes in temperature.
According to the production method of the present invention, a temperature responsive function can be imparted to the surface of an arbitrary base material, and its application range is wide.

  Hereinafter, although the temperature-responsive surface member of the present invention will be specifically described with reference to examples, the present invention is not limited to these examples.

[Synthesis Example 1: Synthesis of amide group-containing polymerizable polymer A of the present invention]
(Step 1)
16 g of DMAc was placed in a 300 mL three-neck flask under a nitrogen atmosphere and stirred at 75 ° C. Among them, 2-hydroxyethyl acrylate (HEA) 3.25 g (0.028 mol), N-isopropylacrylamide (NIPAAm) 13.06 g (0.11 mol), dimethyl 2,2′-azobis (isobutyrate) (V-601) ) A solution of 0.3222 g ((1.4 × 10 ⁻³ mol) dissolved in 16 g of DMAc was added dropwise over 2.5 hours using a plunger pump.
After completion of dropping, the internal temperature was raised from 75 ° C. to 80 ° C. and stirred for 3.0 hours.
Then, it stood to cool to 23 degreeC.

(Step 2)
While stirring the reaction solution, 0.14 g (0.6 × 10 ⁻³ mol) of 2,5-di-tert-amylhydroquinone, 0.18 g (0.3 × 10 ⁻³ mol) of di-n-butyltin dilaurate. mol) was added at 23 ° C.
Thereafter, 9.59 g (0.068 mol) of Karenz AOI and 9.59 g of DMAc were dropped over 5 minutes with a dropping funnel.
After completion of the dropping, the temperature was raised from 23 ° C. to 55 ° C. and stirred for 4.0 hours.
Next, methanol was added and stirred for 1.5 hours.
Then, it stood to cool to 23 degreeC.

(Reprecipitation process)
The reaction solution was dropped into 3 L of distilled water over 1 hour to reprecipitate the target product. Further, reslurry and decantation for 1 hour with 1 L of distilled water were performed twice to obtain polymer A (yield 52.5%). ^The target product was confirmed by ¹ H-NMR, and the polymerization ratio was determined. Moreover, it was 54200 as a result of measuring molecular weight by GPC measurement.
A synthesis scheme is shown below.

[Creation of temperature-responsive surface member]
Example 1
A PET substrate (“Toyobo Ester” film, product name: A4100, thickness: 188 μm, production number: 145102071-3) was cut into 5 cm × 5 cm to prepare a substrate.
The polymerization initiation layer was formed as follows. 1.6 g of methyl ethyl ketone was added and dissolved in 0.4 g of the polymer initiator (B) having the following structure. To this solution, 0.085 g of toluene diisocyanate (TDI) as a cross-linking agent was added, and after stirring and dissolving, it was coated on the PET substrate with a No. 18 bar and dried at 110 ° C. for 10 minutes to form a polymerization initiation layer. did.

As a coating solution for grafting, a 10 wt% acetonitrile solution of polymer A shown in Synthesis Example 1 was prepared. After the preparation, filter filtration (0.2 μ) was performed to obtain a coating solution for grafting.
This grafting coating solution was applied to a PET substrate on which a polymerization initiating layer had been formed with a spin coater under the conditions of (300 rpm / 5 s → 750 rpm / 20 s) and dried at 80 ° C. for 5 minutes.
Next, the substrate was fixed to an adhesion machine, and UV exposure was performed for 0.5 minutes. As the light source, a 1500 W high-pressure mercury lamp (UVX-02516S1LP01, manufactured by Ushio Electric Co., Ltd., light intensity at 254 nm: 38 mW / cm ² ) was used.
After UV exposure, the film was immersed in acetonitrile for 5 minutes for development and dried with an air gun to obtain a temperature-responsive surface member.

(Example 2)
The same substrate as in Example 1 was used as the PET substrate on which the polymerization initiation layer was formed.
A 20 wt% aqueous solution of N-isopropylacrylamide with 0.005 wt% riboflavin added was prepared, and bubbling with nitrogen was performed for 10 minutes to obtain a grafting immersion liquid.
The PET substrate on which the polymerization initiation layer was formed was immersed in a grafting immersion solution, covered with a wrap, and exposed to UV for 0.5 minutes. The same light source as in Example 1 was used.
After UV exposure, it was immersed in distilled water for 30 minutes to remove residual monomers and monomers not bound to PET, and dried with an air gun to obtain a temperature-responsive surface member.

(Comparative Example 1: Electron beam graft polymerization)
This was carried out by the method described in Example 1 of JP-A No. 2004-261532. That is, 0.08 ml of a 30 wt% isopropyl alcohol solution of N-isopropylacrylamide was applied on the same PET substrate (no polymerization initiation layer was formed) as used in Example 1 and Example 2 above. Thereafter, an electron beam having an intensity of 0.25 MGy was irradiated to immobilize the N-isopropylacrylamide polymer on the PET surface. After irradiation, it was immersed in distilled water for 30 minutes to remove residual monomer and monomer not bound to PET, and dried with an air gun to obtain a temperature-responsive surface member.

[Evaluation of contact angle]
The contact angle with respect to the water of the temperature-responsive surface member obtained in Example 1, Example 2, and Comparative Example 1 was 23 ° C. and 50 ° C. using an automatic contact angle measuring device (OCA20) manufactured by Eihiro Seiki Co., Ltd. Measured with The results are shown in Table 1.
All of the temperature-responsive surface members exhibited almost the same contact angle.

[Evaluation of abrasion resistance]
Using the surface of the temperature-responsive surface member obtained in Example 1, Example 2, and Comparative Example 1, a friction tester manufactured by Yasuda Seiki Seisakusho Co., Ltd. (clock meter, friction tester I type, No. 416) was used. Then, the contact angle to water after rubbing 100 times in a wet state (wet wear) under a load of 750 g was measured at 23 ° C. and 50 ° C. using the above contact angle meter. The results are shown in Table 2.

  As is apparent from Table 2, it can be seen that the temperature-responsive surface member of the present invention provides a temperature-responsive surface having high abrasion resistance and excellent durability. Thus, according to the manufacturing method of the present invention, an electron beam irradiation apparatus is not required, and a temperature-responsive surface member having excellent functions and excellent abrasion resistance is produced using a UV exposure apparatus that is a general-purpose apparatus. It turns out that there exists an effect that it can do.

Claims (11)

  A phase transition temperature in the range of 20 to 50 ° C. derived from a compound chemically bonded to the substrate having the polymerization initiating ability and derived from a compound containing an amide group and a polymerizable group in the molecule A temperature-responsive surface member comprising a polymer layer comprising a polymer having the same.   The substrate having the polymerization initiating ability is a substrate having a polymerization initiating layer formed by including a crosslinkable polymerization initiator on the surface of the support, and the crosslinkable polymerization initiator is a heat crosslinkable photoradical polymerization initiator. The temperature-responsive surface member according to claim 1, wherein the polymerizable group in the compound containing an amide group and a polymerizable group in the molecule is a radical polymerizable double bond.   The temperature-responsive surface member according to claim 1 or 2, wherein the compound containing an amide group and a polymerizable group in the molecule is a polymer.   The temperature-responsive surface member according to claim 3, wherein the polymer containing an amide group and a polymerizable group in the molecule is an acrylic polymer.   The temperature responsive surface member according to any one of claims 1 to 4, wherein the amide group is N-isopropylacrylamide.   The temperature-responsive surface member according to any one of claims 2 to 5, wherein the crosslinkable polymerization initiator is a polymer having a crosslinkable group and a polymerization initiating partial structure.   The temperature-responsive surface member according to claim 6, wherein the crosslinkable polymerization initiator is a polymer having a benzophenone structure in the molecule.   The temperature-responsive surface member according to any one of claims 1 to 7, wherein the substrate is a resin film.   The temperature-responsive surface member according to claim 8, wherein the resin film is a resin film made of a polyester resin or a polyimide resin.   (I) a step of bringing a compound having an amide group and a polymerizable group into contact with the surface of a substrate having a polymerization initiating ability; and (II) applying energy to the entire surface or a specific region of the substrate. Forming a polymer layer made of a polymer having an amide group in the region and a phase transition temperature in the range of 20 to 50 ° C., and a method for producing a temperature-responsive surface member.   The substrate having the polymerization initiating ability is provided with a coating liquid layer containing a cross-linkable polymerization initiator on the support, and thereafter, energy is applied to form a cross-linked structure, and polymerization is started on the support surface. The manufacturing method of the temperature-responsive surface member of Claim 10 obtained by forming a layer.