WO2018037816A1 - Method for producing hydrous water absorbent sheet - Google Patents
Method for producing hydrous water absorbent sheet Download PDFInfo
- Publication number
- WO2018037816A1 WO2018037816A1 PCT/JP2017/026983 JP2017026983W WO2018037816A1 WO 2018037816 A1 WO2018037816 A1 WO 2018037816A1 JP 2017026983 W JP2017026983 W JP 2017026983W WO 2018037816 A1 WO2018037816 A1 WO 2018037816A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- absorbent sheet
- photocurable composition
- roll
- sheet
- Prior art date
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- 239000002250 absorbent Substances 0.000 title claims abstract description 80
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- 238000004519 manufacturing process Methods 0.000 title claims description 41
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- ZFOGJHZCXIRTNT-UHFFFAOYSA-O trimethyl-[(prop-2-enoylamino)methyl]azanium Chemical compound C[N+](C)(C)CNC(=O)C=C ZFOGJHZCXIRTNT-UHFFFAOYSA-O 0.000 description 1
- UOASMSQZBFHQGX-UHFFFAOYSA-O trimethyl-[2-(prop-2-enoylamino)ethyl]azanium Chemical compound C[N+](C)(C)CCNC(=O)C=C UOASMSQZBFHQGX-UHFFFAOYSA-O 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/18—Handling of layers or the laminate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
Definitions
- the present invention relates to a method for producing a water-containing water-absorbent sheet.
- Patent Document 1 As water-absorbent sheets such as disposable diapers and pet sheets that require high water absorption, acrylate polymer particles are dispersed on a substrate and fixed with a covering binder (Patent Document 1).
- the water absorbent sheet As a new use of the water absorbent sheet, it is considered to be applied to a window glass or a transparent display. In that case, the haze degree exceeds 8% as a practical transparency for the water absorbent sheet. There is no need for it.
- the conventional water-absorbent sheet is cloudy because the acrylate polymer particles have a particle size relatively larger than the wavelength of visible light, even if a transparent material is used as a base material or a coating binder. There was a problem that the transparency of the polymer particles could be seen, and the desired transparency could not be obtained.
- the conventional water-absorbent sheet is prepared in accordance with a plurality of mutually independent processes such as an acrylate polymer synthesizing process, a particle forming process, a sheet forming process, etc.
- a problem that it is practically impossible to produce a water-absorbent sheet by a roll-to-roll method using the composition.
- An object of the present invention is to solve the above-described problems of the conventional technique, and to enable production of a water-absorbent sheet having high transparency before and after water absorption by a roll-to-roll method.
- the inventor of the present invention has a roll-to-roll method by irradiating a photocurable composition layer containing a hydrophilic monomer that gives a homopolymer having a glass transition temperature of 50 ° C. or higher and further subjecting it to a water treatment. It has been found that a water-containing water-absorbent sheet having water absorption and excellent transparency can be produced. Based on these findings, the present inventor has completed the present invention.
- the present invention is a method for producing a water-containing water-absorbent sheet having transparency by a roll-to-roll method, and includes the following ⁇ Step (A)> to ⁇ Step (E)>: ⁇ Process (A)> Preparing a photocurable composition containing a hydrophilic monomer that gives a homopolymer having a glass transition temperature of 50 ° C.
- ⁇ Process (B)> Applying the photocurable composition to a substrate film drawn from an unwinding roll to form a photocurable composition layer on the substrate film;
- ⁇ Process (C)> A step of irradiating the photocurable composition layer with ultraviolet rays to photocur the photocurable composition layer to form a water absorbent sheet;
- ⁇ Process (D)> A step of forming a water-containing water-absorbent sheet by subjecting the water-absorbent sheet to water treatment; and
- ⁇ Step (E)> A step of winding the water-absorbing water-absorbent sheet on a winding roll together with a base film;
- a water-absorbent sheet is prepared by irradiating a photocurable composition layer containing a hydrophilic monomer that gives a homopolymer having a glass transition temperature of 50 ° C. or higher with ultraviolet rays. Water is added by water treatment. As a result, the obtained water-absorbing water-absorbent sheet can be applied to production by a roll-to-roll method while having good water absorption and excellent transparency.
- FIG. 1 is a schematic view of a roll-to-roll manufacturing apparatus for manufacturing a water-containing water-absorbent sheet.
- the present invention is a method for producing a water-containing water-absorbent sheet having transparency by a roll-to-roll method, and is a production method having the following ⁇ Step (A)> to ⁇ Step (E)>.
- “transparency” means that the haze degree measured in accordance with JIS K7136 is 8% or less, preferably 5% or less.
- “Water absorption” means that the water absorption is 50% by mass or more of the weight of the sheet.
- a known roll-to-roll type sheet production apparatus for example, a sheet production apparatus disclosed in FIG. 5 or FIG. 8 of JP-A-2001-89719) is provided with a hydration means. (See FIG. 1) can be applied.
- the manufacturing apparatus will be described later.
- a photocurable composition containing one or more hydrophilic monomers giving a homopolymer having a glass transition temperature of 50 ° C. or higher is prepared.
- the reason why the hydrophilic monomer is used is to control the water absorption, tackiness in the water absorption state, sheet hardness, roll-to-roll production suitability and the like of the polymer sheet obtained by polymerizing the hydrophilic monomer.
- the hydrophilic monomer contained in the photocurable composition is preferably a monofunctional monomer having a charged monomer or a highly polar substituent. From the viewpoint of the solubility parameter (SP value), the SP value is 19 or more. The monomer which shows is.
- hydrophilic monomer examples include vinyl alcohol, vinyl acetate, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic acid amide and the like.
- a hydrophilic group such as a hydroxy group, a carboxyl group, or a polyether group may be bonded to these hydrophilic monomers as necessary.
- a hydroxyl group-containing (meth) acrylamide preferably hydroxyethyl acrylamide
- (meth) acrylic acid preferably acrylic acid
- a hydroxyl group-containing (meth) acrylic ester preferably hydroxyethyl methacrylate or Hydroxypropyl acrylate etc.
- a (meth) acrylamide quaternary ammonium salt monomer represented by the following formula (1) can be used as the hydrophilic monomer.
- this monomer high water absorption can be imparted to the water-containing water-absorbent sheet of the present invention, and tackiness in the polymer sheet in which the water-containing state is maintained can be suppressed or adjusted.
- R 1 and R 2 are each independently a hydrogen atom or a lower alkyl group.
- R 3 and R 4 are a lower alkyl group,
- R 5 is a lower alkyl group, a lower alkenyl group or a benzyl group,
- A is a lower alkylene group, and
- X ⁇ is a halogen anion or a perchlorate anion.
- examples of the lower alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a Sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Of these, a methyl group is preferred.
- examples of the lower alkenyl group include ethenyl group, 1 or 2-propenyl group, 1,2 or 3-butenyl group, 1,2,3 or 4-pentenyl group, 1,2,3,4, 5-hexenyl group and the like. Can be mentioned.
- Examples of the lower alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.
- Examples of the halogen anion include chloro anion, bromo anion, and iodo anion.
- Preferred R 1 is a hydrogen atom
- preferred R 2 is a methyl group
- preferred R 3 , R 4 and R 5 are methyl groups
- preferred A is a propylene group
- preferred X ⁇ is a chloroanion.
- specific examples of the cation moiety of the (meth) acrylamide-based quaternary ammonium salt monomer include acryloylaminomethyltrimethylammonium, acryloylaminomethyltriethylammonium, acryloylaminomethyltripropylammonium, acryloylaminoethyltrimethylammonium, acryloylaminopropyl.
- Trimethylammonium Trimethylammonium, acryloylaminopropylmethyldiethylammonium, acryloylaminopropylethyldimethylammonium, acryloylaminopropylmethyldipropylammonium, acryloylaminopropyltriethylammonium, acryloylaminopropyltripropylammonium, acryloylaminoethyldimethylbenzylammonium, acryloyl Mino dimethyl benzyl ammonium, acrylamide-based quaternary ammonium cations, such as acryloyl aminopropyl diethyl benzyl ammonium.
- acryloylaminopropyltrimethylammonium and acryloylaminopropyldimethylbenzylammonium are preferred because inexpensive industrial raw materials are easily available. Particularly preferred is acryloylaminopropyltrimethylammonium.
- preferable (meth) acrylamide type quaternary ammonium salt monomer of the formula (1) includes acryloylaminopropyltrimethylammonium chloride, in other words, dimethylaminopropylacrylamide methyl chloride salt.
- the hydrophilic monomer as described above gives a homopolymer having a glass transition temperature measured in accordance with JIS K7121 of 50 ° C. or higher.
- the photocurable composition containing the above hydrophilic monomer can contain a crosslinking agent, a photopolymerization initiator, and other additives.
- Crosslinking agent As a crosslinking agent, a well-known crosslinking agent can be used suitably. Among these, a polyfunctional (meth) acrylate monomer can be preferably used. Specific examples of such a polyfunctional (meth) acrylate monomer include polypropylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol acrylate and the like.
- the content of the polyfunctional (meth) acrylate monomer in the photocurable composition is preferably 0.01 to 5.0 parts by weight, more preferably 0.1 to 2.5 parts by weight with respect to 100 parts by weight of the hydrophilic monomer. Part by mass. Within this range, the water-absorbent sheet can exhibit good water insolubility and water absorbability.
- the photocurable composition can further contain a photopolymerization initiator, particularly a photoradical polymerization initiator, and a water-absorbent sheet having transparency can be obtained by photocuring reaction.
- a radical photopolymerization initiator known ones can be used, for example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, anisole methyl ether; 4 -(2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone (Darocur 2959; BASF Japan Ltd.), ⁇ -hydroxy- ⁇ , ⁇ '-dimethylacetophenone (Darocur 1173; BASF Japan Ltd.) , Methoxyacetophenone, 2,2′-dimethoxy-2-phenylacetophenone (Irgacure 651; BASF Japan Ltd.), 2-
- Propiophenones such as 2-hydroxy-2-methylpropiophenone and 2-hydroxy-4′-isopropyl-2-methylpropiophenone; benzophenone, methylbenzophenone, p-chlorobenzophenone, p-dimethylaminobenzophenone
- Benzophenones such as thioxanthone, 2-chlorothioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2 Thioxanthones such as 4-diisopropylthioxanthone and dodecylthioxanthone; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) ) Acy
- the content of the photopolymerization initiator in the photocurable composition is preferably 0.01 to 5.0 parts by mass, more preferably 0.1 to 2.5 parts by mass with respect to 100 parts by mass of the hydrophilic monomer. is there. If it is this range, sufficient photoreactivity will be acquired, without reaction progressing excessively, and the target transparent water-absorbing sheet can be obtained.
- the photocurable composition contains a transparent thermoplastic resin, an antioxidant, a light stabilizer, a polymerization inhibitor, a silane coupling agent, a dye, a water-soluble antibacterial agent and the like as long as the effects of the present invention are not impaired. be able to.
- a water treatment is performed in the process (D) mentioned later, you may adjust the water content in the case of a water treatment by previously making water contain in a photocurable composition.
- the photo-curable composition can be prepared by mixing a hydrophilic monomer with a crosslinking agent, a photopolymerization initiator and other components and mixing them uniformly by a known method.
- the photocurable composition prepared in the step (A) is applied to the base film drawn from the unwinding roll to form a photocurable composition layer on the base film.
- a coating method a known method can be adopted.
- the coating can be performed using a manufacturing apparatus having a “coating unit” capable of performing a calendar method, a bar coater method, or the like.
- a known sheet used as a support sheet for the water-absorbent sheet can be applied.
- a support sheet a release or non-release polyethylene terephthalate sheet can be preferably used.
- a support sheet it can set suitably according to the manufacturing conditions and intended purpose of a water absorbing sheet.
- Such a support sheet may be peeled off as necessary when the water absorbent sheet is used.
- the photocurable composition layer obtained in the step (B) is photocured to form a water-absorbent sheet having excellent transparency.
- the ultraviolet irradiation can be performed by applying a known ultraviolet irradiation technique. For example, it can be performed by irradiating the photocurable composition layer laminated on the transparent polyethylene terephthalate film subjected to the peeling treatment with ultraviolet rays emitted from a light source such as a chemical lamp or a high-pressure mercury lamp.
- the chemical lamp adjusted to 0.5 to 1.5 mW / cm 2 is irradiated with ultraviolet rays for 5 to 10 minutes, and then 1000 to 1500 mJ / cm 2 with a high-pressure mercury lamp. Irradiation with a light amount is mentioned.
- the transparent protective film which gave the peeling process between the photocurable composition layer and a light source is interposed, or a transparent protective film is closely laminated
- oxygen in the air can be blocked and the photocurable composition layer can be photocured, and good curability can be obtained.
- the water-absorbent sheet is water-containing by subjecting the water-absorbent sheet to a water treatment to obtain a water-containing water-absorbent sheet.
- the obtained water-absorbing water-absorbent sheet becomes flexible and can withstand roll winding.
- hydration treatment method various methods that can supply moisture to the water-absorbent sheet without impairing the effects of the present invention can be employed.
- a method of spraying water on the water-absorbent sheet from a spray nozzle a method of immersing the water-absorbent sheet in water, a method of leaving the water-absorbent polymer sheet in a humidification tank maintained at a saturated water vapor pressure, and the like can be mentioned.
- the water adhering to the surface of the water-containing water-absorbent sheet may be removed by air blow or after scraping with a squeegee.
- the degree of hydration treatment (that is, the water content) in the water-containing water-absorbent sheet is preferably 1 to 50% by mass, more preferably 5 to 20% by mass. If it is this range, the softness
- the said water-containing water absorbing sheet is wound up with a base film on a winding roll.
- the water-containing water-absorbent sheet wound in roll shape can be obtained.
- the water-absorbing water-absorbent sheet thus prepared can be preferably used by being attached to an adherend such as a transparent display after being supported by the base film or after removing the base film.
- FIG. 1 is a schematic view of a production apparatus for carrying out the method for producing a water-containing water-absorbent sheet of the present invention.
- the manufacturing apparatus 100 includes an application unit 40 that applies a photocurable composition, an irradiation unit 70 that irradiates ultraviolet rays, a spray nozzle 60 that is a hydration unit for adding water to the water absorbent sheet, and a surface of the water absorbent sheet.
- An air blow device 80 which is a draining means for removing attached water, and further includes an unwinding unit 30 for supplying the base film 3, a laminating unit 50 for laminating the peeling film 5, and a peeling film 5.
- a peeling roll 96 for peeling, a laminating roll 98 for laminating the peeling protective film 6 provided as necessary, and a winding portion 90 for winding the water-absorbing water-absorbing sheet 4 ′ formed on the base film 3 are provided. is doing.
- the base film 3 is drawn out from the web 34 of the base film 3 mounted on the unwinding shaft 32 of the unwinding section 30 to the coating section 40.
- the coating unit 40 includes a pair of an upper surface roll 42 and a lower surface roll 44, and a dam 46 for supplying the photocurable composition 4a is attached to the lower surface roll 44.
- a predetermined gap 48 is formed between the upper surface roll 42 and the lower surface roll 44, and when the base film 3 passes through the gap 48, the photocurable composition 4 a is applied onto the base film 3, and light A curable composition layer is formed.
- the release film 5 is drawn from a release film web (not shown), placed on the photocurable composition layer, and placed between a pair of upper and lower rolls 52 and 54 of the laminated portion 50. When passing through the gap 58, the release film 5 is laminated on the photocurable composition layer.
- the base film 3 in which the photocurable composition layer and the release film 5 are laminated on the base film 3 is conveyed to an irradiation unit 70 that irradiates ultraviolet rays.
- the irradiation unit 70 is provided with a support roller 73 that supports movement of the release film in a metal irradiation chamber 71 and a light source lamp 72 that irradiates ultraviolet rays as energy rays.
- the photocurable composition layer on the substrate film 3 conveyed into the irradiation chamber 71 starts a polymerization reaction when irradiated with ultraviolet rays from the light source lamp 72, and after completion of the polymerization reaction, the water absorbent sheet 4 It becomes.
- the intensity of the ultraviolet light of the light source lamp 72 is set so that the polymerization reaction is almost completed while the photocurable composition layer passes through the irradiation chamber 71.
- the base film 3 on which the water-absorbent sheet 4 is formed is unloaded from the irradiation unit 70, the release film 5 is peeled off by the peeling roll 96, and the exposed water-absorbent sheet 4 is removed from the spray nozzle 60, which is a hydration means.
- the water is sprayed with water.
- the water absorbent sheet 4 is made to contain water.
- a water-containing water absorbent sheet 4 ' is obtained.
- the water-containing water-absorbing sheet 4 ′ is further blown with air from an air blowing device 80, which is a draining means, if necessary, and the water on the surface is removed.
- the water-containing water-absorbent sheet web 94 is obtained by being wound around the winding shaft 92 of the winding portion 90. Next, by cutting the web 94 into a predetermined size, a desired water-absorbing sheet can be obtained.
- Examples 1 to 3 Comparative Examples 1 to 5 (Preparation of photocurable composition) 100 parts by mass of the photocurable monomer shown in Table 1, 0.3 parts by mass of a photopolymerization initiator (Daroquier 1173, BASF Japan Ltd.), and 0.3 parts by mass of a crosslinking agent (M-400, Toagosei Co., Ltd.) Were uniformly mixed using a rotary blade stirrer (Three-One Motor, Shinto Kagaku Co., Ltd.) to prepare a photocurable composition.
- a photopolymerization initiator Dioquier 1173, BASF Japan Ltd.
- M-400 a crosslinking agent
- This photo-curable composition has a base coat film (38 ⁇ m-thick peeling) unrolled from the unwinding roll of the sheet manufacturing apparatus as shown in FIG. 1 having a bar coater coating unit and employing a roll-to-roll system. It apply
- the photocurable composition layer on which the peeling protective film is laminated is irradiated with ultraviolet rays (main wavelength: 352 nm) from a chemical lamp adjusted to 1 mW / cm 2 for 5 minutes, and then irradiated with ultraviolet rays (main wavelength: 365 nm) from a high-pressure mercury lamp.
- ultraviolet rays main wavelength: 352 nm
- a high-pressure mercury lamp irradiated with ultraviolet rays
- the water-absorbing water-absorbent sheet was cut into a 10 cm square and the release-treated polyethylene terephthalate film was peeled off and heated in an oven set at 135 ° C. for 3 hours, and the water content of the water-absorbing water-absorbing sheet was determined from the weight change rate before and after heating. It was.
- the haze degree of the water-containing water absorbent sheet was measured according to JIS K7136, and evaluated according to the following evaluation criteria.
- the water-absorbent water-absorbing sheets of Examples 1 to 3 using a hydrophilic monomer having a glass transition temperature of 55 ° C. or higher and a hydrotreatment were excellent in transparency and It showed good water absorption. Moreover, it was excellent in roll-to-roll production suitability.
- the water-absorbing water-absorbing sheet of Example 3 using hydroxyethyl methacrylate as the hydrophilic monomer was very excellent in water absorption.
- the water-absorbent sheets of Comparative Examples 4 and 5 using a hydrophilic monomer with a homopolymer glass transition temperature of ⁇ 7 ° C. are substantially in water absorption, transparency, and roll-to-roll production suitability with and without water treatment. No difference was observed.
- the photocurable composition layer containing a hydrophilic monomer that gives a homopolymer having a glass transition temperature of 50 ° C. or higher to an ultraviolet ray after irradiation, Moisture the absorbent sheet.
- the obtained water-absorbing water-absorbent sheet can be applied to production by a roll-to-roll method while having good water absorption and excellent transparency.
Abstract
According to the present invention, a photocurable composition containing a hydrophilic monomer that produces a homopolymer having a glass transition temperature of 50°C or higher is prepared; a photocurable composition layer is formed on a base film pulled out from a feed roll by applying the photocurable composition to the base film; a water absorbent sheet is formed by photocuring the photocurable composition layer by irradiating the photocurable composition layer with ultraviolet light; the water absorbent sheet is caused to contain water by subjecting the water absorbent sheet to a water addition treatment; and the thus-obtained hydrous water absorbent sheet is wound around a take-up roll together with the base film. Consequently, a hydrous water absorbent sheet having good water absorption and excellent transparency is able to be produced by a roll-to-roll process.
Description
本発明は、含水吸水性シートの製造方法に関する。
The present invention relates to a method for producing a water-containing water-absorbent sheet.
高い吸水性が要求される紙おむつやペットシーツ等の吸水性シートとして、アクリル酸塩系ポリマー粒子を基材上に散布し、被覆結合材で固定したものが提案されている（特許文献１）。
As water-absorbent sheets such as disposable diapers and pet sheets that require high water absorption, acrylate polymer particles are dispersed on a substrate and fixed with a covering binder (Patent Document 1).
ところで、吸水性シートの新たな用途として、窓ガラスや透明ディスプレイに適用することが考えられているが、その場合、吸水性シートに対しては、実用的な透明度としてヘイズ度が８％を超えないことが求められている。しかしながら、従来の吸水性シートは、基材や被覆結合材として透明材料を使用したとしても、アクリル酸塩系ポリマー粒子が可視光線の波長よりも相対的に大きな粒径を有するため、白濁して見えたり、ポリマー粒子の外形が見えたりし、所期の透明性が得られないという問題があった。
By the way, as a new use of the water absorbent sheet, it is considered to be applied to a window glass or a transparent display. In that case, the haze degree exceeds 8% as a practical transparency for the water absorbent sheet. There is no need for it. However, the conventional water-absorbent sheet is cloudy because the acrylate polymer particles have a particle size relatively larger than the wavelength of visible light, even if a transparent material is used as a base material or a coating binder. There was a problem that the transparency of the polymer particles could be seen, and the desired transparency could not be obtained.
また、従来の吸水性シートは、アクリル酸塩系ポリマーの合成工程、粒子化工程、シート化工程等の互いに独立した複数の工程に従って作成されており、アクリル酸塩モノマーを含有する光硬化性樹脂組成物を用いて、ロールツーロール（Ｒｏｌｌ－ｔｏ－Ｒｏｌｌ）方式で吸水性シートを製造することが実質的にできないという問題もあった。
In addition, the conventional water-absorbent sheet is prepared in accordance with a plurality of mutually independent processes such as an acrylate polymer synthesizing process, a particle forming process, a sheet forming process, etc. There is also a problem that it is practically impossible to produce a water-absorbent sheet by a roll-to-roll method using the composition.
本発明の目的は、以上の従来の技術の問題点を解決することであり、吸水前後で高い透明性を有する吸水性シートをロールツーロール方式で製造できるようにすることである。
An object of the present invention is to solve the above-described problems of the conventional technique, and to enable production of a water-absorbent sheet having high transparency before and after water absorption by a roll-to-roll method.
本発明者は、ガラス転移温度が５０℃以上のホモポリマーを与える親水性モノマーを含有する光硬化性組成物層に紫外線照射し、更に加水処理を施すことにより、ロールツーロール方式で、良好な吸水性と、優れた透明性とを有する含水吸水性シートを製造できることを見出した。本発明者は、これらの知見に基づき、本発明を完成させるに至った。
The inventor of the present invention has a roll-to-roll method by irradiating a photocurable composition layer containing a hydrophilic monomer that gives a homopolymer having a glass transition temperature of 50 ° C. or higher and further subjecting it to a water treatment. It has been found that a water-containing water-absorbent sheet having water absorption and excellent transparency can be produced. Based on these findings, the present inventor has completed the present invention.
即ち、本発明は、透明性を有する含水吸水性シートをロールツーロール方式で製造する方法であって、以下の＜工程（Ａ）＞～＜工程（Ｅ）＞：
＜工程（Ａ）＞
ガラス転移温度が５０℃以上のホモポリマーを与える親水性モノマーを含有する光硬化性組成物を調製する工程；
＜工程（Ｂ）＞
巻き出しロールから引き出された基材フィルムに前記光硬化性組成物を塗布して、基材フィルム上に光硬化性組成物層を形成する工程；
＜工程（Ｃ）＞
前記光硬化性組成物層に対し紫外線を照射することにより、当該光硬化性組成物層を光硬化させて吸水性シートを形成する工程；
＜工程（Ｄ）＞
前記吸水性シートに対し加水処理を施すことにより、含水吸水性シートを形成する工程；及び
＜工程（Ｅ）＞
前記含水吸水性シートを基材フィルムと共に巻き取りロールに巻き取る工程；
を有することを特徴とする製造方法を提供する。 That is, the present invention is a method for producing a water-containing water-absorbent sheet having transparency by a roll-to-roll method, and includes the following <Step (A)> to <Step (E)>:
<Process (A)>
Preparing a photocurable composition containing a hydrophilic monomer that gives a homopolymer having a glass transition temperature of 50 ° C. or higher;
<Process (B)>
Applying the photocurable composition to a substrate film drawn from an unwinding roll to form a photocurable composition layer on the substrate film;
<Process (C)>
A step of irradiating the photocurable composition layer with ultraviolet rays to photocur the photocurable composition layer to form a water absorbent sheet;
<Process (D)>
A step of forming a water-containing water-absorbent sheet by subjecting the water-absorbent sheet to water treatment; and <Step (E)>
A step of winding the water-absorbing water-absorbent sheet on a winding roll together with a base film;
A manufacturing method characterized by comprising:
＜工程（Ａ）＞
ガラス転移温度が５０℃以上のホモポリマーを与える親水性モノマーを含有する光硬化性組成物を調製する工程；
＜工程（Ｂ）＞
巻き出しロールから引き出された基材フィルムに前記光硬化性組成物を塗布して、基材フィルム上に光硬化性組成物層を形成する工程；
＜工程（Ｃ）＞
前記光硬化性組成物層に対し紫外線を照射することにより、当該光硬化性組成物層を光硬化させて吸水性シートを形成する工程；
＜工程（Ｄ）＞
前記吸水性シートに対し加水処理を施すことにより、含水吸水性シートを形成する工程；及び
＜工程（Ｅ）＞
前記含水吸水性シートを基材フィルムと共に巻き取りロールに巻き取る工程；
を有することを特徴とする製造方法を提供する。 That is, the present invention is a method for producing a water-containing water-absorbent sheet having transparency by a roll-to-roll method, and includes the following <Step (A)> to <Step (E)>:
<Process (A)>
Preparing a photocurable composition containing a hydrophilic monomer that gives a homopolymer having a glass transition temperature of 50 ° C. or higher;
<Process (B)>
Applying the photocurable composition to a substrate film drawn from an unwinding roll to form a photocurable composition layer on the substrate film;
<Process (C)>
A step of irradiating the photocurable composition layer with ultraviolet rays to photocur the photocurable composition layer to form a water absorbent sheet;
<Process (D)>
A step of forming a water-containing water-absorbent sheet by subjecting the water-absorbent sheet to water treatment; and <Step (E)>
A step of winding the water-absorbing water-absorbent sheet on a winding roll together with a base film;
A manufacturing method characterized by comprising:
本発明の含水吸水性シートの製造方法では、ガラス転移温度が５０℃以上のホモポリマーを与える親水性モノマーを含有する光硬化性組成物層に紫外線照射することにより吸水性シートを作成し、更に加水処理を施して含水させる。この結果、得られる含水吸水性シートは、良好な吸水性と、優れた透明性とを有しながらも、ロールツーロール方式での製造に適用可能なものとなる。
In the method for producing a water-containing water-absorbent sheet of the present invention, a water-absorbent sheet is prepared by irradiating a photocurable composition layer containing a hydrophilic monomer that gives a homopolymer having a glass transition temperature of 50 ° C. or higher with ultraviolet rays. Water is added by water treatment. As a result, the obtained water-absorbing water-absorbent sheet can be applied to production by a roll-to-roll method while having good water absorption and excellent transparency.
本発明は、透明性を有する含水吸水性シートをロールツーロール方式で製造する方法であって、以下の＜工程（Ａ）＞～＜工程（Ｅ）＞を有する製造方法である。ここで、「透明性」とは、ＪＩＳ Ｋ７１３６に準拠して測定されたヘイズ度が８％以下、好ましくは５％以下であることを意味する。また、「吸水性」とは、シートの自重の５０質量％以上の吸水率を示すことを意味する。
The present invention is a method for producing a water-containing water-absorbent sheet having transparency by a roll-to-roll method, and is a production method having the following <Step (A)> to <Step (E)>. Here, “transparency” means that the haze degree measured in accordance with JIS K7136 is 8% or less, preferably 5% or less. “Water absorption” means that the water absorption is 50% by mass or more of the weight of the sheet.
なお、本発明の製造方法には、公知のロールツーロール方式のシート製造装置（例えば、特開２００１－８９７１９号の図５又は図８に開示のシート製造装置）に加水手段を設けた製造装置（図１参照）を適用することができる。製造装置については、後述する。
In the production method of the present invention, a known roll-to-roll type sheet production apparatus (for example, a sheet production apparatus disclosed in FIG. 5 or FIG. 8 of JP-A-2001-89719) is provided with a hydration means. (See FIG. 1) can be applied. The manufacturing apparatus will be described later.
＜工程（Ａ）＞
まず、ガラス転移温度が５０℃以上のホモポリマーを与える１種以上の親水性モノマーを含有する光硬化性組成物を調製する。親水性モノマーを使用するのは、それを重合させて得たポリマーシートの吸水性、吸水状態におけるタック性、シート硬さ、ロールツーロール生産適性等をコントロールするためである。 <Process (A)>
First, a photocurable composition containing one or more hydrophilic monomers giving a homopolymer having a glass transition temperature of 50 ° C. or higher is prepared. The reason why the hydrophilic monomer is used is to control the water absorption, tackiness in the water absorption state, sheet hardness, roll-to-roll production suitability and the like of the polymer sheet obtained by polymerizing the hydrophilic monomer.
まず、ガラス転移温度が５０℃以上のホモポリマーを与える１種以上の親水性モノマーを含有する光硬化性組成物を調製する。親水性モノマーを使用するのは、それを重合させて得たポリマーシートの吸水性、吸水状態におけるタック性、シート硬さ、ロールツーロール生産適性等をコントロールするためである。 <Process (A)>
First, a photocurable composition containing one or more hydrophilic monomers giving a homopolymer having a glass transition temperature of 50 ° C. or higher is prepared. The reason why the hydrophilic monomer is used is to control the water absorption, tackiness in the water absorption state, sheet hardness, roll-to-roll production suitability and the like of the polymer sheet obtained by polymerizing the hydrophilic monomer.
（親水性モノマー）
光硬化性組成物が含有する親水性モノマーとしては、電荷を有するモノマーないしは極性の高い置換基を含む好ましくは単官能モノマーであり、溶解度パラメータ（ＳＰ値）の観点からは、ＳＰ値が１９以上を示すモノマーを意味している。 (Hydrophilic monomer)
The hydrophilic monomer contained in the photocurable composition is preferably a monofunctional monomer having a charged monomer or a highly polar substituent. From the viewpoint of the solubility parameter (SP value), the SP value is 19 or more. The monomer which shows is.
光硬化性組成物が含有する親水性モノマーとしては、電荷を有するモノマーないしは極性の高い置換基を含む好ましくは単官能モノマーであり、溶解度パラメータ（ＳＰ値）の観点からは、ＳＰ値が１９以上を示すモノマーを意味している。 (Hydrophilic monomer)
The hydrophilic monomer contained in the photocurable composition is preferably a monofunctional monomer having a charged monomer or a highly polar substituent. From the viewpoint of the solubility parameter (SP value), the SP value is 19 or more. The monomer which shows is.
親水性モノマーの具体例としては、ビニルアルコール、酢酸ビニル、（メタ）アクリル酸、（メタ）アクリル酸エステル、（メタ）アクリル酸アミド等が挙げられる。これらの親水性モノマーには、必要に応じて、ヒドロキシ基、カルボキシル基、ポリエーテル基等の親水性基が結合していてもよい。中でも、吸水性の点から水酸基含有（メタ）アクリルアミド（好ましくはヒドロキシエチルアクリルアミド等）、（メタ）アクリル酸（好ましくはアクリル酸）、又は水酸基含有（メタ）アクリル酸エステル（好ましくはヒドロキシエチルメタクリレートやヒドロキシプロピルアクリレート等）を好ましく使用することができる。
Specific examples of the hydrophilic monomer include vinyl alcohol, vinyl acetate, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic acid amide and the like. A hydrophilic group such as a hydroxy group, a carboxyl group, or a polyether group may be bonded to these hydrophilic monomers as necessary. Among these, from the viewpoint of water absorption, a hydroxyl group-containing (meth) acrylamide (preferably hydroxyethyl acrylamide), (meth) acrylic acid (preferably acrylic acid), or a hydroxyl group-containing (meth) acrylic ester (preferably hydroxyethyl methacrylate or Hydroxypropyl acrylate etc.) can be preferably used.
また、親水性モノマーとして、以下の式（１）の（メタ）アクリルアミド系第４級アンモニウム塩モノマーを使用することもできる。このモノマーを使用した場合には、本発明の含水吸水性シートに対し高吸水性を付与し、また、含水状態が維持されているポリマーシートにおけるタック性を抑制もしくは調整することができる。
Also, a (meth) acrylamide quaternary ammonium salt monomer represented by the following formula (1) can be used as the hydrophilic monomer. When this monomer is used, high water absorption can be imparted to the water-containing water-absorbent sheet of the present invention, and tackiness in the polymer sheet in which the water-containing state is maintained can be suppressed or adjusted.
式（１）中、Ｒ1及びＲ2はそれぞれ独立的に水素原子又は低級アルキル基である。Ｒ3及びＲ4は低級アルキル基であり、Ｒ5は低級アルキル基、低級アルケニル基又はベンジル基であり、Ａは低級アルキレン基であり、X-はハロゲンアニオン又は過塩素酸アニオンである。これらの置換基において、低級アルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、Ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基等が挙げられ、中でもメチル基が好ましい。低級アルケニル基としては、エテニル基、１又は２－プロペニル基、１，２又は３－ブテニル基、１，２，３又は４－ペンテニル基、１，２，３，４又は５－ヘキセニル基等が挙げられる。低級アルキレン基としては、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基等が挙げられる。ハロゲンアニオンとしては、クロロアニオン、ブロモアニオン、イオドアニオンが挙げられる。
In formula (1), R 1 and R 2 are each independently a hydrogen atom or a lower alkyl group. R 3 and R 4 are a lower alkyl group, R 5 is a lower alkyl group, a lower alkenyl group or a benzyl group, A is a lower alkylene group, and X − is a halogen anion or a perchlorate anion. In these substituents, examples of the lower alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a Sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Of these, a methyl group is preferred. Examples of the lower alkenyl group include ethenyl group, 1 or 2-propenyl group, 1,2 or 3-butenyl group, 1,2,3 or 4-pentenyl group, 1,2,3,4, 5-hexenyl group and the like. Can be mentioned. Examples of the lower alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. Examples of the halogen anion include chloro anion, bromo anion, and iodo anion.
好ましいＲ1は水素原子であり、好ましいＲ2はメチル基であり、好ましいＲ3、Ｒ4及びＲ5はメチル基であり、好ましいＡはプロピレン基であり、好ましいX-はクロロアニオンである。
Preferred R 1 is a hydrogen atom, preferred R 2 is a methyl group, preferred R 3 , R 4 and R 5 are methyl groups, preferred A is a propylene group, and preferred X − is a chloroanion.
一方、（メタ）アクリルアミド系第４級アンモニウム塩モノマーのカチオン部の具体例としては、アクリロイルアミノメチルトリメチルアンモニウム、アクリロイルアミノメチルトリエチルアンモニウム、アクリロイルアミノメチルトリプロピルアンモニウム、アクリロイルアミノエチルトリメチルアンモニウム、アクリロイルアミノプロピルトリメチルアンモニウム、アクリロイルアミノプロピルメチルジエチルアンモニウム、アクリロイルアミノプロピルエチルジメチルアンモニウム、アクリロイルアミノプロピルメチルジプロピルアンモニウム、アクリロイルアミノプロピルトリエチルアンモニウム、アクリロイルアミノプロピルトリプロピルアンモニウム、アクリロイルアミノエチルジメチルベンジルアンモニウム、アクリロイルアミノプロピルジメチルベンジルアンモニウム、アクリロイルアミノプロピルジエチルベンジルアンモニウムなどのアクリルアミド系第４級アンモニウムカチオンが挙げられる。中でも安価な工業的原料を入手しやすい点で、アクリロイルアミノプロピルトリメチルアンモニウム、アクリロイルアミノプロピルジメチルベンジルアンモニウムが好ましい。特に好ましくは、アクリロイルアミノプロピルトリメチルアンモニウムである。
On the other hand, specific examples of the cation moiety of the (meth) acrylamide-based quaternary ammonium salt monomer include acryloylaminomethyltrimethylammonium, acryloylaminomethyltriethylammonium, acryloylaminomethyltripropylammonium, acryloylaminoethyltrimethylammonium, acryloylaminopropyl. Trimethylammonium, acryloylaminopropylmethyldiethylammonium, acryloylaminopropylethyldimethylammonium, acryloylaminopropylmethyldipropylammonium, acryloylaminopropyltriethylammonium, acryloylaminopropyltripropylammonium, acryloylaminoethyldimethylbenzylammonium, acryloyl Mino dimethyl benzyl ammonium, acrylamide-based quaternary ammonium cations, such as acryloyl aminopropyl diethyl benzyl ammonium. Of these, acryloylaminopropyltrimethylammonium and acryloylaminopropyldimethylbenzylammonium are preferred because inexpensive industrial raw materials are easily available. Particularly preferred is acryloylaminopropyltrimethylammonium.
従って、好ましい式（１）の（メタ）アクリルアミド系第４級アンモニウム塩モノマーとしては、アクリロイルアミノプロピルトリメチルアンモニウムクロライド、換言すれば、ジメチルアミノプロピルアクリルアミド塩化メチル塩が挙げられる。
Therefore, preferable (meth) acrylamide type quaternary ammonium salt monomer of the formula (1) includes acryloylaminopropyltrimethylammonium chloride, in other words, dimethylaminopropylacrylamide methyl chloride salt.
また、本発明においては、以上説明したような親水性モノマーは、ＪＩＳ Ｋ７１２１に準拠して測定したガラス転移温度が５０℃以上のホモポリマーを与えるものである。
In the present invention, the hydrophilic monomer as described above gives a homopolymer having a glass transition temperature measured in accordance with JIS K7121 of 50 ° C. or higher.
（光硬化性組成物）
以上の親水性モノマーを含有する光硬化性組成物は、架橋剤、光重合開始剤、その他の添加剤を含有することができる。 (Photocurable composition)
The photocurable composition containing the above hydrophilic monomer can contain a crosslinking agent, a photopolymerization initiator, and other additives.
以上の親水性モノマーを含有する光硬化性組成物は、架橋剤、光重合開始剤、その他の添加剤を含有することができる。 (Photocurable composition)
The photocurable composition containing the above hydrophilic monomer can contain a crosslinking agent, a photopolymerization initiator, and other additives.
（架橋剤）
架橋剤としては、公知の架橋剤を適宜使用することができる。中でも、多官能（メタ）アクリレートモノマーを好ましく使用することができる。このような多官能（メタ）アクリレートモノマーの具体例としては、ポリプレピレングリコールジアクリレート、ポリエチレングリコールジアクリレート、ジペンタエリスリトールアクリレート等を挙げることができる。 (Crosslinking agent)
As a crosslinking agent, a well-known crosslinking agent can be used suitably. Among these, a polyfunctional (meth) acrylate monomer can be preferably used. Specific examples of such a polyfunctional (meth) acrylate monomer include polypropylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol acrylate and the like.
架橋剤としては、公知の架橋剤を適宜使用することができる。中でも、多官能（メタ）アクリレートモノマーを好ましく使用することができる。このような多官能（メタ）アクリレートモノマーの具体例としては、ポリプレピレングリコールジアクリレート、ポリエチレングリコールジアクリレート、ジペンタエリスリトールアクリレート等を挙げることができる。 (Crosslinking agent)
As a crosslinking agent, a well-known crosslinking agent can be used suitably. Among these, a polyfunctional (meth) acrylate monomer can be preferably used. Specific examples of such a polyfunctional (meth) acrylate monomer include polypropylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol acrylate and the like.
多官能（メタ）アクリレートモノマーの光硬化性組成物中の含有量は、親水性モノマー１００質量部に対し、好ましくは０．０１～５．０質量部、より好ましくは０．１～２．５質量部である。この範囲であれば、吸水性シートに良好な水不溶性と水吸収性とを発現させることができる。
The content of the polyfunctional (meth) acrylate monomer in the photocurable composition is preferably 0.01 to 5.0 parts by weight, more preferably 0.1 to 2.5 parts by weight with respect to 100 parts by weight of the hydrophilic monomer. Part by mass. Within this range, the water-absorbent sheet can exhibit good water insolubility and water absorbability.
（光重合開始剤）
光硬化性組成物は、更に、光重合開始剤、特に光ラジカル重合開始剤を含有することができ、光硬化反応させることで透明性を有する吸水性シートを得ることができる。このような光ラジカル重合開始剤としては、公知のものを使用することができ、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、アニソールメチルエーテルなどのベンゾイン類；４－（２－ヒドロキシエトキシ）フェニル（２－ヒドロキシ－２－プロピル）ケトン（ダロキュアー２９５９；ＢＡＳＦジャパン（株））、α－ヒドロキシ－α、α'－ジメチルアセトフェノン（ダロキュアー１１７３；ＢＡＳＦジャパン（株））、メトキシアセトフェノン、２，２'－ジメトキシ－２－フェニルアセトフェノン（イルガキュアー６５１；ＢＡＳＦジャパン（株））、２－ヒドロキシ－２－シクロヘキシルアセトフェノン（イルガキュアー１８４；ＢＡＳＦジャパン（株））、２，２－ジエトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、４－フェノキシジクロロアセトフェノン、４－ｔ－ブチル－ジクロロアセトフェノンなどのアセトフェノン類；２－ヒドロキシ－２－メチルプロピオフェノン、２－ヒドロキシ－４'－イソプロピル－２－メチルプロピオフェノンなどのプロピオフェノン類；ベンゾフェノン、メチルベンゾフェノン、ｐ－クロルベンゾフェノン、ｐ－ジメチルアミノベンゾフェノンなどのベンゾフェノン類；チオキサントン、２－クロルチオキサントン、２－エチルチオキサントン、２－イソプロピルチオキサントン、２，４－ジクロロチオキサントン、２，４－ジエチルチオキサントン、２，４－ジイソプロピルチオキサントン、ドデシルチオキサントンなどのチオキサントン類；ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－２，４－ジ－ｎ－ブトキシフェニルフォスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルフェニルフォスフィンオキサイドなどのアシルフォスフィンオキサイド類；ベンジル、ジベンゾスベロン、α－アシルオキシムエステルなどが挙げられる。 (Photopolymerization initiator)
The photocurable composition can further contain a photopolymerization initiator, particularly a photoradical polymerization initiator, and a water-absorbent sheet having transparency can be obtained by photocuring reaction. As such a radical photopolymerization initiator, known ones can be used, for example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, anisole methyl ether; 4 -(2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone (Darocur 2959; BASF Japan Ltd.), α-hydroxy-α, α'-dimethylacetophenone (Darocur 1173; BASF Japan Ltd.) , Methoxyacetophenone, 2,2′-dimethoxy-2-phenylacetophenone (Irgacure 651; BASF Japan Ltd.), 2-hydroxy-2-cyclohexylacetophenone (Irgacure 184; B SF Japan Ltd.), 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, etc. Propiophenones such as 2-hydroxy-2-methylpropiophenone and 2-hydroxy-4′-isopropyl-2-methylpropiophenone; benzophenone, methylbenzophenone, p-chlorobenzophenone, p-dimethylaminobenzophenone Benzophenones such as thioxanthone, 2-chlorothioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2 Thioxanthones such as 4-diisopropylthioxanthone and dodecylthioxanthone; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) ) Acylphosphine oxides such as -2,4-di-n-butoxyphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphenylphosphine oxide; benzyl, dibenzos Examples include beron and α-acyl oxime ester.
光硬化性組成物は、更に、光重合開始剤、特に光ラジカル重合開始剤を含有することができ、光硬化反応させることで透明性を有する吸水性シートを得ることができる。このような光ラジカル重合開始剤としては、公知のものを使用することができ、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、アニソールメチルエーテルなどのベンゾイン類；４－（２－ヒドロキシエトキシ）フェニル（２－ヒドロキシ－２－プロピル）ケトン（ダロキュアー２９５９；ＢＡＳＦジャパン（株））、α－ヒドロキシ－α、α'－ジメチルアセトフェノン（ダロキュアー１１７３；ＢＡＳＦジャパン（株））、メトキシアセトフェノン、２，２'－ジメトキシ－２－フェニルアセトフェノン（イルガキュアー６５１；ＢＡＳＦジャパン（株））、２－ヒドロキシ－２－シクロヘキシルアセトフェノン（イルガキュアー１８４；ＢＡＳＦジャパン（株））、２，２－ジエトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、４－フェノキシジクロロアセトフェノン、４－ｔ－ブチル－ジクロロアセトフェノンなどのアセトフェノン類；２－ヒドロキシ－２－メチルプロピオフェノン、２－ヒドロキシ－４'－イソプロピル－２－メチルプロピオフェノンなどのプロピオフェノン類；ベンゾフェノン、メチルベンゾフェノン、ｐ－クロルベンゾフェノン、ｐ－ジメチルアミノベンゾフェノンなどのベンゾフェノン類；チオキサントン、２－クロルチオキサントン、２－エチルチオキサントン、２－イソプロピルチオキサントン、２，４－ジクロロチオキサントン、２，４－ジエチルチオキサントン、２，４－ジイソプロピルチオキサントン、ドデシルチオキサントンなどのチオキサントン類；ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－２，４－ジ－ｎ－ブトキシフェニルフォスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルフェニルフォスフィンオキサイドなどのアシルフォスフィンオキサイド類；ベンジル、ジベンゾスベロン、α－アシルオキシムエステルなどが挙げられる。 (Photopolymerization initiator)
The photocurable composition can further contain a photopolymerization initiator, particularly a photoradical polymerization initiator, and a water-absorbent sheet having transparency can be obtained by photocuring reaction. As such a radical photopolymerization initiator, known ones can be used, for example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, anisole methyl ether; 4 -(2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone (Darocur 2959; BASF Japan Ltd.), α-hydroxy-α, α'-dimethylacetophenone (Darocur 1173; BASF Japan Ltd.) , Methoxyacetophenone, 2,2′-dimethoxy-2-phenylacetophenone (Irgacure 651; BASF Japan Ltd.), 2-hydroxy-2-cyclohexylacetophenone (Irgacure 184; B SF Japan Ltd.), 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, etc. Propiophenones such as 2-hydroxy-2-methylpropiophenone and 2-hydroxy-4′-isopropyl-2-methylpropiophenone; benzophenone, methylbenzophenone, p-chlorobenzophenone, p-dimethylaminobenzophenone Benzophenones such as thioxanthone, 2-chlorothioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2 Thioxanthones such as 4-diisopropylthioxanthone and dodecylthioxanthone; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) ) Acylphosphine oxides such as -2,4-di-n-butoxyphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphenylphosphine oxide; benzyl, dibenzos Examples include beron and α-acyl oxime ester.
光重合開始剤の光硬化性組成物中の含有量は、親水性モノマー１００質量部に対し、好ましくは０．０１～５．０質量部、より好ましくは０．１～２．５質量部である。この範囲であれば、過度に反応が進むことなく十分な光反応性が得られ、目的の透明な吸水性シートを得ることができる。
The content of the photopolymerization initiator in the photocurable composition is preferably 0.01 to 5.0 parts by mass, more preferably 0.1 to 2.5 parts by mass with respect to 100 parts by mass of the hydrophilic monomer. is there. If it is this range, sufficient photoreactivity will be acquired, without reaction progressing excessively, and the target transparent water-absorbing sheet can be obtained.
（その他の成分）
光硬化性組成物は、本発明の効果を損なわない範囲で、透明な熱可塑性樹脂、酸化防止剤、光安定剤、重合禁止剤、シランカップリング剤、染料、水溶性抗菌剤等を含有することができる。また、後述する工程（Ｄ）において加水処理を行うものの、予め光硬化性組成物に水を含有させて、加水処理の際の水分量を調整しても良い。 (Other ingredients)
The photocurable composition contains a transparent thermoplastic resin, an antioxidant, a light stabilizer, a polymerization inhibitor, a silane coupling agent, a dye, a water-soluble antibacterial agent and the like as long as the effects of the present invention are not impaired. be able to. Moreover, although a water treatment is performed in the process (D) mentioned later, you may adjust the water content in the case of a water treatment by previously making water contain in a photocurable composition.
光硬化性組成物は、本発明の効果を損なわない範囲で、透明な熱可塑性樹脂、酸化防止剤、光安定剤、重合禁止剤、シランカップリング剤、染料、水溶性抗菌剤等を含有することができる。また、後述する工程（Ｄ）において加水処理を行うものの、予め光硬化性組成物に水を含有させて、加水処理の際の水分量を調整しても良い。 (Other ingredients)
The photocurable composition contains a transparent thermoplastic resin, an antioxidant, a light stabilizer, a polymerization inhibitor, a silane coupling agent, a dye, a water-soluble antibacterial agent and the like as long as the effects of the present invention are not impaired. be able to. Moreover, although a water treatment is performed in the process (D) mentioned later, you may adjust the water content in the case of a water treatment by previously making water contain in a photocurable composition.
光硬化性組成物は、親水性モノマーに、架橋剤、光重合開始剤やその他の成分を混合し、公知の手法により均一に混合することにより調製することができる。
The photo-curable composition can be prepared by mixing a hydrophilic monomer with a crosslinking agent, a photopolymerization initiator and other components and mixing them uniformly by a known method.
＜工程（Ｂ）＞
次に、工程（Ａ）で調製した光硬化性組成物を、巻き出しロールから引き出された基材フィルムに塗布して、基材フィルム上に光硬化性組成物層を形成する。塗布の方法としては、公知の手法を採用することができ、例えば、カレンダー法やバーコータ法等を実施可能な「塗布ユニット」を有する製造装置を使って塗布することができる。 <Process (B)>
Next, the photocurable composition prepared in the step (A) is applied to the base film drawn from the unwinding roll to form a photocurable composition layer on the base film. As a coating method, a known method can be adopted. For example, the coating can be performed using a manufacturing apparatus having a “coating unit” capable of performing a calendar method, a bar coater method, or the like.
次に、工程（Ａ）で調製した光硬化性組成物を、巻き出しロールから引き出された基材フィルムに塗布して、基材フィルム上に光硬化性組成物層を形成する。塗布の方法としては、公知の手法を採用することができ、例えば、カレンダー法やバーコータ法等を実施可能な「塗布ユニット」を有する製造装置を使って塗布することができる。 <Process (B)>
Next, the photocurable composition prepared in the step (A) is applied to the base film drawn from the unwinding roll to form a photocurable composition layer on the base film. As a coating method, a known method can be adopted. For example, the coating can be performed using a manufacturing apparatus having a “coating unit” capable of performing a calendar method, a bar coater method, or the like.
基材フィルムとしては、吸水性シートの支持シートとして使用されている公知のシートを適用することができる。このような支持シートとしては、剥離処理又は未剥離処理ポリエチレンテレフタレートシートを好ましく使用できる。支持シートの厚みについては、吸水性シートの製造条件や使用目的に応じて適宜設定することができる。このような支持シートは、吸水性シートの使用時に、必要に応じて剥離してもよい。
As the base film, a known sheet used as a support sheet for the water-absorbent sheet can be applied. As such a support sheet, a release or non-release polyethylene terephthalate sheet can be preferably used. About the thickness of a support sheet, it can set suitably according to the manufacturing conditions and intended purpose of a water absorbing sheet. Such a support sheet may be peeled off as necessary when the water absorbent sheet is used.
＜工程（Ｃ）＞
次に、工程（Ｂ）で得られた前記光硬化性組成物層に対し紫外線を照射することにより、当該光硬化性組成物層を光硬化させて透明性に優れた吸水性シートを形成する。紫外線照射は、公知の紫外線照射技術を適用して行うことができる。例えば、剥離処理された透明ポリエチレンテレフタレートフィルムに積層された光硬化性組成物層に対し、ケミカルランプ、高圧水銀ランプ等の光源が発した紫外線を照射することにより行うことができる。紫外線の照射条件の一例としては、０．５～１．５ｍＷ／ｃｍ2に調整されたケミカルランプで５～１０分間紫外線を照射し、続いて、高圧水銀ランプで１０００～１５００ｍＪ／ｃｍ2の積算光量で照射することが挙げられる。 <Process (C)>
Next, by irradiating the photocurable composition layer obtained in the step (B) with ultraviolet rays, the photocurable composition layer is photocured to form a water-absorbent sheet having excellent transparency. . The ultraviolet irradiation can be performed by applying a known ultraviolet irradiation technique. For example, it can be performed by irradiating the photocurable composition layer laminated on the transparent polyethylene terephthalate film subjected to the peeling treatment with ultraviolet rays emitted from a light source such as a chemical lamp or a high-pressure mercury lamp. As an example of the irradiation condition of ultraviolet rays, the chemical lamp adjusted to 0.5 to 1.5 mW / cm 2 is irradiated with ultraviolet rays for 5 to 10 minutes, and then 1000 to 1500 mJ / cm 2 with a high-pressure mercury lamp. Irradiation with a light amount is mentioned.
次に、工程（Ｂ）で得られた前記光硬化性組成物層に対し紫外線を照射することにより、当該光硬化性組成物層を光硬化させて透明性に優れた吸水性シートを形成する。紫外線照射は、公知の紫外線照射技術を適用して行うことができる。例えば、剥離処理された透明ポリエチレンテレフタレートフィルムに積層された光硬化性組成物層に対し、ケミカルランプ、高圧水銀ランプ等の光源が発した紫外線を照射することにより行うことができる。紫外線の照射条件の一例としては、０．５～１．５ｍＷ／ｃｍ2に調整されたケミカルランプで５～１０分間紫外線を照射し、続いて、高圧水銀ランプで１０００～１５００ｍＪ／ｃｍ2の積算光量で照射することが挙げられる。 <Process (C)>
Next, by irradiating the photocurable composition layer obtained in the step (B) with ultraviolet rays, the photocurable composition layer is photocured to form a water-absorbent sheet having excellent transparency. . The ultraviolet irradiation can be performed by applying a known ultraviolet irradiation technique. For example, it can be performed by irradiating the photocurable composition layer laminated on the transparent polyethylene terephthalate film subjected to the peeling treatment with ultraviolet rays emitted from a light source such as a chemical lamp or a high-pressure mercury lamp. As an example of the irradiation condition of ultraviolet rays, the chemical lamp adjusted to 0.5 to 1.5 mW / cm 2 is irradiated with ultraviolet rays for 5 to 10 minutes, and then 1000 to 1500 mJ / cm 2 with a high-pressure mercury lamp. Irradiation with a light amount is mentioned.
なお、紫外線照射の際に、光硬化性組成物層と光源との間に剥離処理を施した透明保護フィルムを介在させるか、または光硬化性組成物層に透明保護フィルムを密着積層させる。これにより、空気中の酸素を遮断して光硬化性組成物層を光硬化させることができ、良好な硬化性を得ることができる。
In addition, in the case of ultraviolet irradiation, the transparent protective film which gave the peeling process between the photocurable composition layer and a light source is interposed, or a transparent protective film is closely laminated | stacked on a photocurable composition layer. Thereby, oxygen in the air can be blocked and the photocurable composition layer can be photocured, and good curability can be obtained.
＜工程（Ｄ）＞
次に、前記吸水性シートに対し加水処理を施すことにより、吸水性シートに含水させ、含水吸水性シートを得る。得られた含水吸水性シートは、シート自体が柔軟となり、ロール巻きに耐えられるようになる。 <Process (D)>
Next, the water-absorbent sheet is water-containing by subjecting the water-absorbent sheet to a water treatment to obtain a water-containing water-absorbent sheet. The obtained water-absorbing water-absorbent sheet becomes flexible and can withstand roll winding.
次に、前記吸水性シートに対し加水処理を施すことにより、吸水性シートに含水させ、含水吸水性シートを得る。得られた含水吸水性シートは、シート自体が柔軟となり、ロール巻きに耐えられるようになる。 <Process (D)>
Next, the water-absorbent sheet is water-containing by subjecting the water-absorbent sheet to a water treatment to obtain a water-containing water-absorbent sheet. The obtained water-absorbing water-absorbent sheet becomes flexible and can withstand roll winding.
加水処理の手法としては、本発明の効果を損なわずに吸水性シートに水分を供給できる種々の手法を採用することができる。例えば、スプレーノズルから水を吸水性シートに噴霧する方法、水中に吸水性シートを浸漬する方法、飽和水蒸気圧に保たれた加湿槽に吸水性ポリマーシートを放置する方法等を挙げることができる。なお、必要に応じ、加水処理後に、含水吸水性シートの表面に付着している水をエアブローにより除去してもよく、スキージにより掻き取ってもよい。
As the hydration treatment method, various methods that can supply moisture to the water-absorbent sheet without impairing the effects of the present invention can be employed. For example, a method of spraying water on the water-absorbent sheet from a spray nozzle, a method of immersing the water-absorbent sheet in water, a method of leaving the water-absorbent polymer sheet in a humidification tank maintained at a saturated water vapor pressure, and the like can be mentioned. If necessary, the water adhering to the surface of the water-containing water-absorbent sheet may be removed by air blow or after scraping with a squeegee.
含水吸水性シートにおける加水処理の程度（即ち、含水率）は、好ましくは１～５０質量％、より好ましくは５～２０質量％である。この範囲であればロールツーロールで製造可能な柔軟性を吸水性シートに付与することができる。
The degree of hydration treatment (that is, the water content) in the water-containing water-absorbent sheet is preferably 1 to 50% by mass, more preferably 5 to 20% by mass. If it is this range, the softness | flexibility which can be manufactured by roll-to-roll can be provided to a water absorbing sheet.
＜工程（Ｅ）＞
次に、前記含水吸水性シートを基材フィルムと共に巻き取りロールに巻き取る。これによりロール状に巻かれた含水吸水性シートを得ることができる。このように作成された含水吸水性シートは、基材フィルムに支持されたまま、あるいは基材フィルムを取り除いた後、透明ディスプレイ等の被着物に貼り付けて好ましく使用することができる。 <Process (E)>
Next, the said water-containing water absorbing sheet is wound up with a base film on a winding roll. Thereby, the water-containing water-absorbent sheet wound in roll shape can be obtained. The water-absorbing water-absorbent sheet thus prepared can be preferably used by being attached to an adherend such as a transparent display after being supported by the base film or after removing the base film.
次に、前記含水吸水性シートを基材フィルムと共に巻き取りロールに巻き取る。これによりロール状に巻かれた含水吸水性シートを得ることができる。このように作成された含水吸水性シートは、基材フィルムに支持されたまま、あるいは基材フィルムを取り除いた後、透明ディスプレイ等の被着物に貼り付けて好ましく使用することができる。 <Process (E)>
Next, the said water-containing water absorbing sheet is wound up with a base film on a winding roll. Thereby, the water-containing water-absorbent sheet wound in roll shape can be obtained. The water-absorbing water-absorbent sheet thus prepared can be preferably used by being attached to an adherend such as a transparent display after being supported by the base film or after removing the base film.
（本発明の製造方法の適用例）
図１は、本発明の含水吸水性シートの製造方法を実施するための製造装置の概略図である。この製造装置１００は、光硬化性組成物を塗布する塗布部４０と、紫外線を照射する照射部７０と、吸水性シートに加水するための加水手段であるスプレーノズル６０と、吸水性シート表面に付着した水を除去するための水切り手段であるエアブロー装置８０とを有し、更に、基材フィルム３を供給する巻出し部３０と、剥離フィルム５を積層する積層部５０と、剥離フィルム５を剥離する剥離ロール９６と、必要に応じて設けられる剥離保護フィルム６を積層する積層ロール９８と、基材フィルム上３に形成された含水吸水性シート４´を巻き取る巻取り部９０とを有している。 (Application example of the production method of the present invention)
FIG. 1 is a schematic view of a production apparatus for carrying out the method for producing a water-containing water-absorbent sheet of the present invention. Themanufacturing apparatus 100 includes an application unit 40 that applies a photocurable composition, an irradiation unit 70 that irradiates ultraviolet rays, a spray nozzle 60 that is a hydration unit for adding water to the water absorbent sheet, and a surface of the water absorbent sheet. An air blow device 80 which is a draining means for removing attached water, and further includes an unwinding unit 30 for supplying the base film 3, a laminating unit 50 for laminating the peeling film 5, and a peeling film 5. A peeling roll 96 for peeling, a laminating roll 98 for laminating the peeling protective film 6 provided as necessary, and a winding portion 90 for winding the water-absorbing water-absorbing sheet 4 ′ formed on the base film 3 are provided. is doing.
図１は、本発明の含水吸水性シートの製造方法を実施するための製造装置の概略図である。この製造装置１００は、光硬化性組成物を塗布する塗布部４０と、紫外線を照射する照射部７０と、吸水性シートに加水するための加水手段であるスプレーノズル６０と、吸水性シート表面に付着した水を除去するための水切り手段であるエアブロー装置８０とを有し、更に、基材フィルム３を供給する巻出し部３０と、剥離フィルム５を積層する積層部５０と、剥離フィルム５を剥離する剥離ロール９６と、必要に応じて設けられる剥離保護フィルム６を積層する積層ロール９８と、基材フィルム上３に形成された含水吸水性シート４´を巻き取る巻取り部９０とを有している。 (Application example of the production method of the present invention)
FIG. 1 is a schematic view of a production apparatus for carrying out the method for producing a water-containing water-absorbent sheet of the present invention. The
この製造装置１００においては、まず、巻出し部３０の巻出し軸３２に装着された基材フィルム３のウエブ３４から基材フィルム３が、塗布部４０まで引き出される。
In this manufacturing apparatus 100, first, the base film 3 is drawn out from the web 34 of the base film 3 mounted on the unwinding shaft 32 of the unwinding section 30 to the coating section 40.
塗布部４０は、上面ロール４２と下面ロール４４とが一対に配置され、下面ロール４４には光硬化性組成物４ａを供給するためのダム４６が付設されている。
The coating unit 40 includes a pair of an upper surface roll 42 and a lower surface roll 44, and a dam 46 for supplying the photocurable composition 4a is attached to the lower surface roll 44.
上面ロール４２と下面ロール４４の間には所定の間隙４８が形成され、基材フィルム３が前記間隙４８を通過する際に、光硬化性組成物４ａが基材フィルム３上に塗布され、光硬化性組成物層が形成される。
A predetermined gap 48 is formed between the upper surface roll 42 and the lower surface roll 44, and when the base film 3 passes through the gap 48, the photocurable composition 4 a is applied onto the base film 3, and light A curable composition layer is formed.
次に、剥離フィルム５が、剥離フィルムウエブ（図示せず）から引き出され、光硬化性組成物層上に載置され、積層部５０の一対に配置された上面ロール５２と下面ロール５４との間隙５８を通過する際に、光硬化性組成物層上に剥離フィルム５が積層される。
Next, the release film 5 is drawn from a release film web (not shown), placed on the photocurable composition layer, and placed between a pair of upper and lower rolls 52 and 54 of the laminated portion 50. When passing through the gap 58, the release film 5 is laminated on the photocurable composition layer.
基材フィルム３上に光硬化性組成物層と剥離フィルム５とが積層された基材フィルム３は、紫外線を照射する照射部７０に搬送される。ここで、照射部７０には、金属製の照射室７１中に剥離フィルムの移動を支持する支持ローラ７３と、エネルギー線として紫外線を照射する光源ランプ７２とが配備されている。照射室７１内に搬送された基材フィルム３上の光硬化性組成物層は、上記光源ランプ７２から紫外線が照射されると、それにより重合反応を開始し、重合反応終了後に吸水性シート４となる。なお、光源ランプ７２の紫外線の強度は、光硬化性組成物層が照射室７１を通過する間に重合反応がほぼ完了するように設定されている。
The base film 3 in which the photocurable composition layer and the release film 5 are laminated on the base film 3 is conveyed to an irradiation unit 70 that irradiates ultraviolet rays. Here, the irradiation unit 70 is provided with a support roller 73 that supports movement of the release film in a metal irradiation chamber 71 and a light source lamp 72 that irradiates ultraviolet rays as energy rays. The photocurable composition layer on the substrate film 3 conveyed into the irradiation chamber 71 starts a polymerization reaction when irradiated with ultraviolet rays from the light source lamp 72, and after completion of the polymerization reaction, the water absorbent sheet 4 It becomes. The intensity of the ultraviolet light of the light source lamp 72 is set so that the polymerization reaction is almost completed while the photocurable composition layer passes through the irradiation chamber 71.
次に、吸水性シート４が形成された基材フィルム３は照射部７０から搬出され、剥離ロール９６で剥離フィルム５が剥離され、露出した吸水性シート４は、加水手段であるスプレーノズル６０からの水の噴霧により加水処理が施される。これにより吸水性シート４に含水させる。この結果、含水吸水性シート４′が得られる。この含水吸水性シート４′は、更に必要に応じて水切り手段であるエアブロー装置８０からエアが吹き付けられ、その表面の水が除去され、更に、必要に応じて剥離保護フィルム６が積層され、更に、巻取り部９０の巻取り軸９２により巻き取られ、含水吸水性シートウエブ９４が得られる。つぎに、このウエブ９４を所定の大きさに裁断することにより、目的の含水吸水性シートを得ることができる。
Next, the base film 3 on which the water-absorbent sheet 4 is formed is unloaded from the irradiation unit 70, the release film 5 is peeled off by the peeling roll 96, and the exposed water-absorbent sheet 4 is removed from the spray nozzle 60, which is a hydration means. The water is sprayed with water. Thereby, the water absorbent sheet 4 is made to contain water. As a result, a water-containing water absorbent sheet 4 'is obtained. The water-containing water-absorbing sheet 4 ′ is further blown with air from an air blowing device 80, which is a draining means, if necessary, and the water on the surface is removed. Further, if necessary, the peeling protective film 6 is laminated, The water-containing water-absorbent sheet web 94 is obtained by being wound around the winding shaft 92 of the winding portion 90. Next, by cutting the web 94 into a predetermined size, a desired water-absorbing sheet can be obtained.
以下、本発明を実施例により具体的に説明する。
Hereinafter, the present invention will be specifically described with reference to examples.
実施例１～３、比較例１～５
（光硬化性組成物の調製）
表１の光硬化性モノマー１００質量部、光重合開始剤（ダロキユアー１１７３、ＢＡＳＦジャパン（株））０．３質量部、及び架橋剤（Ｍ－４００、東亞合成（株））０．３質量部を回転翼式撹拌機（スリーワンモータ、新東科学（株））を用いて均一に混合して、光硬化性組成物を調製した。 Examples 1 to 3, Comparative Examples 1 to 5
(Preparation of photocurable composition)
100 parts by mass of the photocurable monomer shown in Table 1, 0.3 parts by mass of a photopolymerization initiator (Daroquier 1173, BASF Japan Ltd.), and 0.3 parts by mass of a crosslinking agent (M-400, Toagosei Co., Ltd.) Were uniformly mixed using a rotary blade stirrer (Three-One Motor, Shinto Kagaku Co., Ltd.) to prepare a photocurable composition.
（光硬化性組成物の調製）
表１の光硬化性モノマー１００質量部、光重合開始剤（ダロキユアー１１７３、ＢＡＳＦジャパン（株））０．３質量部、及び架橋剤（Ｍ－４００、東亞合成（株））０．３質量部を回転翼式撹拌機（スリーワンモータ、新東科学（株））を用いて均一に混合して、光硬化性組成物を調製した。 Examples 1 to 3, Comparative Examples 1 to 5
(Preparation of photocurable composition)
100 parts by mass of the photocurable monomer shown in Table 1, 0.3 parts by mass of a photopolymerization initiator (Daroquier 1173, BASF Japan Ltd.), and 0.3 parts by mass of a crosslinking agent (M-400, Toagosei Co., Ltd.) Were uniformly mixed using a rotary blade stirrer (Three-One Motor, Shinto Kagaku Co., Ltd.) to prepare a photocurable composition.
（吸水性シートの製造）
この光硬化性組成物を、バーコータ法の塗布ユニットを有し、且つロールツーロール方式を採用した図１のようなシート製造装置の巻き出しロールから巻き出された基材フィルム（３８μｍ厚の剥離処理ポリエチレンテレフタレートフィルム（３８ＧＳ、リンテック（株）））に、前述の塗布ユニットを用いて２００μｍ厚に塗布し、光硬化性組成物層を形成した。その上に基材フィルムと同様の剥離処理ポリエチレンテレフタレートフィルムを剥離保護フィルムとして積層した。 (Manufacture of water absorbent sheets)
This photo-curable composition has a base coat film (38 μm-thick peeling) unrolled from the unwinding roll of the sheet manufacturing apparatus as shown in FIG. 1 having a bar coater coating unit and employing a roll-to-roll system. It apply | coated to the process polyethylene terephthalate film (38GS, Lintec Co., Ltd.) in thickness of 200 micrometers using the above-mentioned application unit, and formed the photocurable composition layer. A release-treated polyethylene terephthalate film similar to the base film was laminated thereon as a release protective film.
この光硬化性組成物を、バーコータ法の塗布ユニットを有し、且つロールツーロール方式を採用した図１のようなシート製造装置の巻き出しロールから巻き出された基材フィルム（３８μｍ厚の剥離処理ポリエチレンテレフタレートフィルム（３８ＧＳ、リンテック（株）））に、前述の塗布ユニットを用いて２００μｍ厚に塗布し、光硬化性組成物層を形成した。その上に基材フィルムと同様の剥離処理ポリエチレンテレフタレートフィルムを剥離保護フィルムとして積層した。 (Manufacture of water absorbent sheets)
This photo-curable composition has a base coat film (38 μm-thick peeling) unrolled from the unwinding roll of the sheet manufacturing apparatus as shown in FIG. 1 having a bar coater coating unit and employing a roll-to-roll system. It apply | coated to the process polyethylene terephthalate film (38GS, Lintec Co., Ltd.) in thickness of 200 micrometers using the above-mentioned application unit, and formed the photocurable composition layer. A release-treated polyethylene terephthalate film similar to the base film was laminated thereon as a release protective film.
剥離保護フィルムが積層された光硬化性組成物層に対し、１ｍＷ／ｃｍ2に調整したケミカルランプから紫外線（主波長３５２ｎｍ）を５分間照射し、続いて高圧水銀ランプから紫外線（主波長３６５ｎｍ）を１０００ｍＪ／ｃｍ2の積算光量となるように照射することにより光硬化させて吸水性シートを作成した。
The photocurable composition layer on which the peeling protective film is laminated is irradiated with ultraviolet rays (main wavelength: 352 nm) from a chemical lamp adjusted to 1 mW / cm 2 for 5 minutes, and then irradiated with ultraviolet rays (main wavelength: 365 nm) from a high-pressure mercury lamp. Was cured by photoirradiation so as to obtain an integrated light amount of 1000 mJ / cm 2 to prepare a water absorbent sheet.
（含水吸水性シートの製造）
吸水性シートの表面を覆っていた剥離保護フィルムを除去し、露出した吸水性シートに対し、スプレーノズルから蒸留水を噴霧し、吸水性シートの含水率が１～５０質量％となるように加水処理を行い、エアブローにより表面に付着していた水を除去し、続いて表面保護シートを加水処理面に積層し、シート製造装置の巻き取りロールに巻き取った。これによりロールに巻かれた含水吸水性シートを得た。 (Manufacture of hydrous water-absorbent sheet)
The release protective film covering the surface of the water-absorbent sheet is removed, and the exposed water-absorbent sheet is sprayed with distilled water from a spray nozzle so that the water content of the water-absorbent sheet is 1 to 50% by mass. Treatment was performed to remove water adhering to the surface by air blowing, and then a surface protection sheet was laminated on the hydrotreated surface and wound on a take-up roll of a sheet manufacturing apparatus. As a result, a water-containing water-absorbent sheet wound around a roll was obtained.
吸水性シートの表面を覆っていた剥離保護フィルムを除去し、露出した吸水性シートに対し、スプレーノズルから蒸留水を噴霧し、吸水性シートの含水率が１～５０質量％となるように加水処理を行い、エアブローにより表面に付着していた水を除去し、続いて表面保護シートを加水処理面に積層し、シート製造装置の巻き取りロールに巻き取った。これによりロールに巻かれた含水吸水性シートを得た。 (Manufacture of hydrous water-absorbent sheet)
The release protective film covering the surface of the water-absorbent sheet is removed, and the exposed water-absorbent sheet is sprayed with distilled water from a spray nozzle so that the water content of the water-absorbent sheet is 1 to 50% by mass. Treatment was performed to remove water adhering to the surface by air blowing, and then a surface protection sheet was laminated on the hydrotreated surface and wound on a take-up roll of a sheet manufacturing apparatus. As a result, a water-containing water-absorbent sheet wound around a roll was obtained.
＜評価＞
得られた含水吸水性シートの加水処理による「含水率」を以下に説明するように測定した。また、含水吸水性シートの「吸水性」を以下に説明するように試験し、評価した。更に、含水吸水性シートの「透明性」について、以下に説明するようにへイズ度を測定し評価した。加えて、ロールツーロール生産適性について以下のように評価した。 <Evaluation>
The “water content” of the obtained water-absorbing water-absorbent sheet was measured as described below. Further, the “water absorption” of the water-containing water absorbent sheet was tested and evaluated as described below. Further, the “transparency” of the water-containing water-absorbent sheet was evaluated by measuring the degree of haze as described below. In addition, the roll-to-roll production suitability was evaluated as follows.
得られた含水吸水性シートの加水処理による「含水率」を以下に説明するように測定した。また、含水吸水性シートの「吸水性」を以下に説明するように試験し、評価した。更に、含水吸水性シートの「透明性」について、以下に説明するようにへイズ度を測定し評価した。加えて、ロールツーロール生産適性について以下のように評価した。 <Evaluation>
The “water content” of the obtained water-absorbing water-absorbent sheet was measured as described below. Further, the “water absorption” of the water-containing water absorbent sheet was tested and evaluated as described below. Further, the “transparency” of the water-containing water-absorbent sheet was evaluated by measuring the degree of haze as described below. In addition, the roll-to-roll production suitability was evaluated as follows.
（加水処理による「含水率」の確認）
含水吸水性シートを１０ｃｍ角に切り出し、剥離処理ポリエチレンテレフタレートフィルムを剥がしたものを１３５℃に設定されたオーブンで３時間加熱し、加熱前後の重量変化率より、含水吸水性シートの含水率を求めた。 (Confirmation of “moisture content” by water treatment)
The water-absorbing water-absorbent sheet was cut into a 10 cm square and the release-treated polyethylene terephthalate film was peeled off and heated in an oven set at 135 ° C. for 3 hours, and the water content of the water-absorbing water-absorbing sheet was determined from the weight change rate before and after heating. It was.
含水吸水性シートを１０ｃｍ角に切り出し、剥離処理ポリエチレンテレフタレートフィルムを剥がしたものを１３５℃に設定されたオーブンで３時間加熱し、加熱前後の重量変化率より、含水吸水性シートの含水率を求めた。 (Confirmation of “moisture content” by water treatment)
The water-absorbing water-absorbent sheet was cut into a 10 cm square and the release-treated polyethylene terephthalate film was peeled off and heated in an oven set at 135 ° C. for 3 hours, and the water content of the water-absorbing water-absorbing sheet was determined from the weight change rate before and after heating. It was.
（吸水性）
含水吸水性シートを精製水３０ｍｌ中に２４時間浸漬し、浸漬前後のシート質量（浸漬前の質量をＷ０、浸漬後の質量をＷ１）を測定し、式「吸水率（％）＝[（Ｗ１－Ｗ０）／Ｗ０]×１００」に従って吸水率を求め、吸水性を以下のように評価した。実用上、吸水率は５０％以上であることが望まれる。 (Water absorption)
The water-absorbing water-absorbing sheet is immersed in 30 ml of purified water for 24 hours, and the sheet mass before and after immersion (the mass before immersion is W0 and the mass after immersion is W1) is measured, and the formula “water absorption (%) = [(W1 The water absorption was determined according to “−W0) / W0] × 100” and the water absorption was evaluated as follows. Practically, the water absorption is desired to be 50% or more.
含水吸水性シートを精製水３０ｍｌ中に２４時間浸漬し、浸漬前後のシート質量（浸漬前の質量をＷ０、浸漬後の質量をＷ１）を測定し、式「吸水率（％）＝[（Ｗ１－Ｗ０）／Ｗ０]×１００」に従って吸水率を求め、吸水性を以下のように評価した。実用上、吸水率は５０％以上であることが望まれる。 (Water absorption)
The water-absorbing water-absorbing sheet is immersed in 30 ml of purified water for 24 hours, and the sheet mass before and after immersion (the mass before immersion is W0 and the mass after immersion is W1) is measured, and the formula “water absorption (%) = [(W1 The water absorption was determined according to “−W0) / W0] × 100” and the water absorption was evaluated as follows. Practically, the water absorption is desired to be 50% or more.
評価基準
〇（良好）： 吸水率が５０％以上である場合
×（不良）： 吸水率が５０％未満である場合 Evaluation criteria ○ (good): When the water absorption is 50% or more × (poor): When the water absorption is less than 50%
〇（良好）： 吸水率が５０％以上である場合
×（不良）： 吸水率が５０％未満である場合 Evaluation criteria ○ (good): When the water absorption is 50% or more × (poor): When the water absorption is less than 50%
（透明性）
含水吸水性シートのヘイズ度をＪＩＳ Ｋ７１３６に準拠して測定し、以下の評価基準に従って評価した。 (transparency)
The haze degree of the water-containing water absorbent sheet was measured according to JIS K7136, and evaluated according to the following evaluation criteria.
含水吸水性シートのヘイズ度をＪＩＳ Ｋ７１３６に準拠して測定し、以下の評価基準に従って評価した。 (transparency)
The haze degree of the water-containing water absorbent sheet was measured according to JIS K7136, and evaluated according to the following evaluation criteria.
評価基準
〇： ヘイズ度が８％以下である場合
△： ヘイズ度が８％超１０％以下である場合
×： ヘイズ度が１０％超である場合 Evaluation criteria ○: When the haze degree is 8% or less △: When the haze degree is more than 8% and 10% or less ×: When the haze degree is more than 10%
〇： ヘイズ度が８％以下である場合
△： ヘイズ度が８％超１０％以下である場合
×： ヘイズ度が１０％超である場合 Evaluation criteria ○: When the haze degree is 8% or less △: When the haze degree is more than 8% and 10% or less ×: When the haze degree is more than 10%
（ロールツーロール生産適性）
含水吸水性シートのロールツーロール生産適性について、含水吸水性シートを３インチ紙管に巻取り、含水吸水性シートにカールやシート割れが発生するか否かを、以下の評価基準に従って評価した。 (Roll-to-roll production suitability)
Regarding the roll-to-roll production suitability of the water-containing water-absorbent sheet, the water-absorbent water-absorbent sheet was wound around a 3-inch paper tube, and whether the water-containing water-absorbent sheet was curled or cracked was evaluated according to the following evaluation criteria.
含水吸水性シートのロールツーロール生産適性について、含水吸水性シートを３インチ紙管に巻取り、含水吸水性シートにカールやシート割れが発生するか否かを、以下の評価基準に従って評価した。 (Roll-to-roll production suitability)
Regarding the roll-to-roll production suitability of the water-containing water-absorbent sheet, the water-absorbent water-absorbent sheet was wound around a 3-inch paper tube, and whether the water-containing water-absorbent sheet was curled or cracked was evaluated according to the following evaluation criteria.
評価基準
〇： カールやシート割れを発生させることなく、３インチ紙管に巻取り可能な場合
△： ３インチ紙管に巻取り可能であるが、カールが発生する場合
×： ３インチ紙管に巻取った場合にシート割れが生じる場合 Evaluation Criteria 〇: Can be wound on a 3 inch paper tube without causing curling or sheet breakage △: Can be wound on a 3 inch paper tube, but curl occurs ×: On a 3 inch paper tube When sheet cracking occurs when winding
〇： カールやシート割れを発生させることなく、３インチ紙管に巻取り可能な場合
△： ３インチ紙管に巻取り可能であるが、カールが発生する場合
×： ３インチ紙管に巻取った場合にシート割れが生じる場合 Evaluation Criteria 〇: Can be wound on a 3 inch paper tube without causing curling or sheet breakage △: Can be wound on a 3 inch paper tube, but curl occurs ×: On a 3 inch paper tube When sheet cracking occurs when winding
表１から分かるように、ホモポリマーのガラス転移温度が５５℃以上となる親水性モノマーを使用し、しかも加水処理を施した実施例１～３の含水吸水性シートは、透明性に優れ、しかも良好な吸水性を示していた。しかもロールツーロール生産適性にも優れていた。特に、親水性モノマーとしてヒドロキシエチルメタクリレートを使用した実施例３の含水吸水性シートは吸水性が非常に優れていた。
As can be seen from Table 1, the water-absorbent water-absorbing sheets of Examples 1 to 3 using a hydrophilic monomer having a glass transition temperature of 55 ° C. or higher and a hydrotreatment were excellent in transparency and It showed good water absorption. Moreover, it was excellent in roll-to-roll production suitability. In particular, the water-absorbing water-absorbing sheet of Example 3 using hydroxyethyl methacrylate as the hydrophilic monomer was very excellent in water absorption.
それに対し、比較例１～３の吸水性シートは、実施例１～３と同じ親水性モノマーを使用していたのにかかわらず、加水処理を施していないので、ロールツーロール生産適性が劣っていた。
On the other hand, the water-absorbent sheets of Comparative Examples 1 to 3 were inferior in roll-to-roll production suitability because they were not subjected to water treatment despite using the same hydrophilic monomers as in Examples 1 to 3. It was.
なお、ホモポリマーのガラス転移温度が－７℃となる親水性モノマーを使用した比較例４，５の吸水性シートは、加水処理の有無で、吸水率、透明性、ロールツーロール生産適性に実質的な差は観察されなかった。
The water-absorbent sheets of Comparative Examples 4 and 5 using a hydrophilic monomer with a homopolymer glass transition temperature of −7 ° C. are substantially in water absorption, transparency, and roll-to-roll production suitability with and without water treatment. No difference was observed.
本発明の含水吸水性シートの製造方法においては、ガラス転移温度が５０℃以上のホモポリマーを与える親水性モノマーを含有する光硬化性組成物層に紫外線照射した後で加水処理を施すことにより、吸水性シートに含水させる。この結果、得られる含水吸水性シートは、良好な吸水性と、優れた透明性とを有しながらも、ロールツーロール方式での製造に適用可能なものとなる。
In the method for producing a water-containing water-absorbent sheet according to the present invention, by subjecting the photocurable composition layer containing a hydrophilic monomer that gives a homopolymer having a glass transition temperature of 50 ° C. or higher to an ultraviolet ray after irradiation, Moisture the absorbent sheet. As a result, the obtained water-absorbing water-absorbent sheet can be applied to production by a roll-to-roll method while having good water absorption and excellent transparency.
３ 基材フィルム
４´ 含水吸水性シート
５ 剥離フィルム
６ 剥離保護フィルム
３０ 巻出し部
４０ 塗布部
５０ 積層部
６０ スプレーノズル
７０ 照射部
８０ エアブロー装置
９０ 巻取り部
９６ 剥離ロール
９８ 積層ロール
１００ 製造装置 DESCRIPTION OFSYMBOLS 3 Base film 4 'Water-containing water absorbing sheet 5 Peeling film 6 Peeling protective film 30 Unwinding part 40 Application part 50 Laminating part 60 Spray nozzle 70 Irradiation part 80 Air blow apparatus 90 Winding part 96 Peeling roll 98 Laminating roll 100 Manufacturing apparatus
４´ 含水吸水性シート
５ 剥離フィルム
６ 剥離保護フィルム
３０ 巻出し部
４０ 塗布部
５０ 積層部
６０ スプレーノズル
７０ 照射部
８０ エアブロー装置
９０ 巻取り部
９６ 剥離ロール
９８ 積層ロール
１００ 製造装置 DESCRIPTION OF
Claims (5)
- 透明性を有する含水吸水性シートをロールツーロール方式で製造する方法であって、以下の＜工程（Ａ）＞～＜工程（Ｅ）＞：
＜工程（Ａ）＞
ガラス転移温度が５０℃以上のホモポリマーを与える親水性モノマーを含有する光硬化性組成物を調製する工程；
＜工程（Ｂ）＞
巻き出しロールから引き出された基材フィルムに前記光硬化性組成物を塗布して、基材フィルム上に光硬化性組成物層を形成する工程；
＜工程（Ｃ）＞
前記光硬化性組成物層に対し紫外線を照射することにより、当該光硬化性組成物層を光硬化させて吸水性シートを形成する工程；
＜工程（Ｄ）＞
前記吸水性シートに対し加水処理を施すことにより、含水吸水性シートを形成する工程；及び
＜工程（Ｅ）＞
前記含水吸水性シートを基材フィルムと共に巻き取りロールに巻き取る工程；
を有することを特徴とする製造方法。 A method for producing a water-containing water-absorbent sheet having transparency by a roll-to-roll method, comprising the following <Step (A)> to <Step (E)>:
<Process (A)>
Preparing a photocurable composition containing a hydrophilic monomer that gives a homopolymer having a glass transition temperature of 50 ° C. or higher;
<Process (B)>
Applying the photocurable composition to a substrate film drawn from an unwinding roll to form a photocurable composition layer on the substrate film;
<Process (C)>
A step of irradiating the photocurable composition layer with ultraviolet rays to photocur the photocurable composition layer to form a water absorbent sheet;
<Process (D)>
A step of forming a water-containing water-absorbent sheet by subjecting the water-absorbent sheet to water treatment; and <Step (E)>
A step of winding the water-absorbing water-absorbent sheet on a winding roll together with a base film;
The manufacturing method characterized by having. - 工程（Ｄ）における加水処理が、スプレーノズルにより水を噴霧することである請求項１記載の製造方法。 The manufacturing method according to claim 1, wherein the water treatment in step (D) is to spray water with a spray nozzle.
- 工程（Ｄ）における含水吸水性シートの含水率が、１～５０質量％である請求項１又は２記載の製造方法。 The production method according to claim 1 or 2, wherein the water content of the water-absorbing water-absorbent sheet in step (D) is 1 to 50 mass%.
- 工程（Ａ）における親水性モノマーが、水酸基含有（メタ）アクリルアミド、（メタ）アクリル酸、又は水酸基含有（メタ）アクリル酸エステルである請求項１～３のいずれかに記載の製造方法。 The process according to any one of claims 1 to 3, wherein the hydrophilic monomer in step (A) is a hydroxyl group-containing (meth) acrylamide, (meth) acrylic acid, or a hydroxyl group-containing (meth) acrylic ester.
- 工程（Ａ）における光硬化性組成物が、更に光重合開始剤と架橋剤とを含有する請求項１～４のいずれかに記載の製造方法。 The production method according to any one of claims 1 to 4, wherein the photocurable composition in the step (A) further contains a photopolymerization initiator and a crosslinking agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016164400A JP2018030308A (en) | 2016-08-25 | 2016-08-25 | Method for producing hydrous water-absorbing sheet |
| JP2016-164400 | 2016-08-25 |
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| Publication Number | Publication Date |
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| WO2018037816A1 true WO2018037816A1 (en) | 2018-03-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/JP2017/026983 WO2018037816A1 (en) | 2016-08-25 | 2017-07-26 | Method for producing hydrous water absorbent sheet |
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| JP (1) | JP2018030308A (en) |
| TW (1) | TW201819487A (en) |
| WO (1) | WO2018037816A1 (en) |
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| CN108582807A (en) * | 2018-03-24 | 2018-09-28 | 常州斯威克光伏新材料有限公司 | A kind of preparation method of soft package lithium battery shell encapsulation aluminum-plastic composite membrane |
| US11773236B2 (en) | 2018-09-27 | 2023-10-03 | Lg Chem, Ltd. | Method of preparing superabsorbent polymer sheet |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020067662A1 (en) * | 2018-09-27 | 2020-04-02 | 주식회사 엘지화학 | Manufacturing method for superabsorbent polymer sheet |
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Also Published As
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| JP2018030308A (en) | 2018-03-01 |
| TW201819487A (en) | 2018-06-01 |
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