CN110418818A - Cast sheet and its manufacturing method and secondary forming product - Google Patents
Cast sheet and its manufacturing method and secondary forming product Download PDFInfo
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- CN110418818A CN110418818A CN201880018448.2A CN201880018448A CN110418818A CN 110418818 A CN110418818 A CN 110418818A CN 201880018448 A CN201880018448 A CN 201880018448A CN 110418818 A CN110418818 A CN 110418818A
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- slurry
- cast sheet
- methyl methacrylate
- based polymer
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- 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
- C08F2/02—Polymerisation in bulk
-
- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention provides the cast sheet and its manufacturing method that can implement bending machining and deep-draw deep processing etc. with higher dimensional accuracy.Cast sheet of the invention includes Methacrylic resin composition, which contains the citrate (D) that the boiling point under noncrosslinking methyl methacrylate based polymer (P), crosslinked methyl methacrylate based polymer (C) and 0.53kPa is 150 DEG C or more.Cast sheet of the invention can manufacture by the following method: prepare the slurry (S) for containing the monomer (M) comprising methyl methacrylate and noncrosslinking methyl methacrylate based polymer (P), obtained raw mixture is carried out cast polymerization by the citrate (D) for being 150 DEG C or more to the boiling point being added under the monomer (M3) and 0.53kPa comprising methyl methacrylate and crosslinking agent in slurry (S).
Description
Technical field
The present invention relates to cast sheet and its manufacturing method and secondary forming product.
Background technique
The transparency, coloring, formability, weatherability and the surface hardness of Methacrylic resin composition etc. are excellent,
Apply flexibly these characteristics and extensive in various fields as signboard, ornament materials, illuminating cover, automobile component and glazing materia etc.
It uses.In turn, in recent years, it as the purposes of metha crylic resin expands, is also gradually defended in bathtub, bathroom and washroom etc.
It is used in the kitchens such as top plate of bath field and whole kitchen field etc..
Different, the bending sections such as formed products and the signboard that is made of mostly plane for bathroom field and kitchen field etc.
It is more.In addition, be not only the simple shape for stretching the central portion of plate along a direction and forming bowl shape etc, with having
Walking auxiliary tool and universal design (also referred to as accessible) without step etc. and designer's article etc. it is universal, it is more complicated
The requirement of diversified shape also increasingly increase.Therefore, for the metha crylic resin combination for these purposes
Object, it is desirable that the higher shaping processability of bending machining and deep-draw deep processing etc. can be easy to carry out.
Metha crylic resinogen is originally thermoplastic resin, therefore bending machining can be carried out by heating, but its
It is to be easy necking down in heating stretches, be difficult to carry out the resin of deep-draw deep processing etc..By using include crosslinked methacrylic acid
The Methacrylic resin composition of methyl esters (MMA) based polymer, shaping processability are improved, and deep-draw deep processing etc. becomes
It may.As the manufacturing method of the formed products comprising being crosslinked MMA based polymer, following methods can be enumerated: to comprising noncrosslinking
In the prepolymerization slurry or dissolution slurry of MMA based polymer and more than one the monomer containing MMA, one containing MMA is added
Kind or more monomer and crosslinking agent, and carry out cast polymerization (for example, the 0026th section etc. of patent document 1).
Existing technical literature
Patent document
Patent document 1: International Publication No. 2015/122174
Summary of the invention
Problem to be solved by the invention
By using the Methacrylic resin composition comprising being crosslinked MMA based polymer, shaping processability is changed
It is kind, still, in order to cope with the requirement of more complicated diversified shape, preferably it can implement to be bent with higher dimensional accuracy
Processing and deep-draw deep processing etc. can be inhibited in bending section and coupled extension section with higher level because of uneven thickness
Caused bad order.
It is curved the present invention has been made in view of the above-described circumstances, and an object thereof is to provide that can be implemented with higher dimensional accuracy
The cast sheet and its manufacturing method of Qu Jiagong and deep-draw deep processing etc..
It should be noted that cast sheet of the invention preferably forms bending in implementation bending machining and deep-draw deep processing etc.
It is used in the case where portion, but can be used for arbitrary purposes.
The method for solving problem
The cast sheet and its manufacturing method of present invention offer [1] below~[5] and secondary forming product.
[1] a kind of cast sheet, it includes Methacrylic resin composition, which contains
Have under noncrosslinking methyl methacrylate based polymer (P), crosslinked methyl methacrylate based polymer (C) and 0.53kPa
Boiling point be 150 DEG C or more of citrate (D).
[2] a kind of manufacturing method of the cast sheet of [1], wherein
Prepare to contain monomer (M) and noncrosslinking methyl methacrylate based polymer comprising methyl methacrylate
(P) slurry (S),
To the boiling point being added in slurry (S) under the monomer (M3) and 0.53kPa comprising methyl methacrylate and crosslinking agent
For 150 DEG C or more of citrates (D),
Obtained raw mixture is subjected to cast polymerization.
[3] according to the manufacturing method of the cast sheet of [2], wherein slurry (S) is containing making comprising methyl methacrylate
The prepolymerization slurry (S1) of noncrosslinking methyl methacrylate based polymer (P1) obtained from monomer (M1) polymerization.
[4] according to the manufacturing method of the cast sheet of [2], wherein slurry (S) is to make noncrosslinking methyl methacrylate system
Dissolution slurry (S2) obtained from polymer (P2) is dissolved in the monomer comprising methyl methacrylate (M2).
[5] a kind of secondary forming product, are made of the cast sheet of [1].
Invention effect
According to the present invention it is possible to provide the casting that can implement bending machining and deep-draw deep processing etc. with higher dimensional accuracy
Mould plate and its manufacturing method.
Specific embodiment
The present invention is described in detail below.It should be noted that in the present specification, sometimes by " methacrylic acid
System " and " acrylic acid series " are collectively referred to as " (methyl) acrylic acid series ".About " (methyl) acrylic acid " and " (methyl) acryloyl group ",
Equally.
[cast sheet]
Cast sheet of the invention includes to contain noncrosslinking methyl methacrylate (MMA) based polymer (P), cross-linked methyl
The metering system for the citrate (D) that boiling point under methyl acrylate (MMA) based polymer (C) and 0.53kPa is 150 DEG C or more
Sour based resin composition.
Cast sheet of the invention can be suitable in the bathrooms field such as bathtub, bathroom and washroom and whole kitchen
Formed products used in the kitchens such as top plate field etc..The thickness of cast sheet can come depending on the application it is appropriately designed, in bathroom field and
Preferably 1~20mm, kitchen field etc. is more preferably 1~10mm on the way.
[manufacturing method of cast sheet]
Cast sheet of the invention can for example be manufactured by following manufacturing methods, and the manufacturing method includes:
Process (1): prepare to contain more than one the monomer (M) comprising methyl methacrylate (MMA) and noncrosslinking
The slurry (S) of methyl methacrylate (MMA) based polymer (P)；
Process (2): to be added in slurry (S) various of monomer (M3) comprising methyl methacrylate (MMA) and crosslinking agent,
And the citrate (D) that the boiling point under 0.53kPa is 150 DEG C or more, obtain raw mixture；With
Process (3): obtained raw mixture is subjected to cast polymerization.
(process (1))
As the preparation method of slurry (S), preferably pre-polymerization is legal and polymer dissolution method.
The slurry (S) obtained by previous method is containing by making more than one monomer (M1) In comprising MMA
Noncrosslinking straight-chain MMA based polymer (P1) and unreacted list obtained from prepolymerization in the presence of polymerization initiator
The prepolymerization slurry (S1) of body (M1).It should be noted that packet will can also further be added into the prepolymerization slurry (S1)
Slurry obtained from more than one monomer (M1) containing MMA and dilution is used as prepolymerization slurry (S1).
The slurry (S) obtained by latter approach is that more than one the monomer polymerization comprising MMA will be used to obtain
Noncrosslinking straight-chain MMA based polymer (P2) be dissolved in more than one the monomer (M2) comprising MMA obtained from it is molten
It solves slurry (S2).
Noncrosslinking MMA based polymer (P) (preferably (P1) or (P2)) can be the homopolymer of MMA, MMA and more than one
The copolymers of other alkyl methacrylates, more than one the alkyl methacrylate comprising MMA and others one
Kind or more copolymerizable unsaturated monomer any one of copolymer.
What it is as the raw material as noncrosslinking straight-chain MMA based polymer (P) (preferably (P1) or (P2)) includes MMA's
More than one monomer (M) (preferably (M1) or (M2)), can enumerate the alkyl methacrylates such as MMA and can be with methacrylic acid
Other copolymerizable unsaturated monomers that Arrcostab is applied in combination.
The carbon atom number of the alkyl of above-mentioned alkyl methacrylate is preferably 1~20, more preferably 1~12.As institute
Alkyl methacrylate is stated, MMA, ethyl methacrylate, n propyl methacrylate, methacrylic acid isopropyl can be enumerated
Ester, n-BMA, Isobutyl methacrylate, 2-Ethylhexyl Methacrylate, lauryl methacrylate and
Cyclohexyl methacrylate etc..
As the other copolymerizable unsaturated monomers that can be applied in combination with alkyl methacrylate, can enumerate: acrylic acid
The propylene such as methyl esters, ethyl acrylate, propyl acrylate, 2-EHA, lauryl acrylate and cyclohexyl acrylate
Acid alkyl ester；(methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 4- hydroxybutyl and (methyl) acrylic acid 2- hydroxyl -3-
Chlorine propyl ester etc. (methyl) hydroxyalkyl acrylates；(methyl) acrylic acid；(methyl) acrylate metal salt；Vinyl chloride, acetic acid second
The vinyl monomers such as enester and vinyltoluene；Acrylonitrile；Acrylamide；The polystyrenes such as styrene and α-methylstyrene
Monomer；Maleic anhydride etc..
Noncrosslinking MMA based polymer (P) in slurry (S) (preferably prepolymerization slurry (S1) or dissolution slurry (S2))
Concentration is not particularly limited, preferably 5~40 mass %, more preferably 5~30 mass %.Noncrosslinking straight-chain MMA system is poly-
The weight average molecular weight (Mw) for closing object (P) is not particularly limited, in the case where prepolymerization slurry (S1), preferably 100,000~150
Ten thousand, 700,000~1,200,000, in the case where dissolving slurry (S2), preferably 50,000~150,000 are more preferably.Weight average molecular weight (Mw)
When to be more than above-mentioned lower limit value, the durabilities such as chemical-resistant become well, when below for upper limit value, the system of slurry (S)
It makes and becomes easy.
The aggregate rate of prepolymerization slurry (S1) is not particularly limited, and preferably 5~40%, more preferably 5~30%.Polymerization
When rate is less than 5%, the heating elongation of resin declines, it is possible to which the bending for being difficult to carry out under the high dimensional accuracy as target adds
Work and deep-draw deep processing etc..When aggregate rate is more than 40%, the viscosity of slurry becomes excessively high, it is possible to be difficult to be added the molten of agent
The evenly dispersed of solution, pigment etc., deaeration and injection to mold etc..Here, " aggregate rate " is monomer used in polymerization reaction
Quality relative to investment monomer quality ratio.
Also slurry or gel comprising partial cross-linked MMA system gelatinous polymer can be used to replace prepolymerization slurry
(S1) or slurry (S2) is dissolved.The slurry or gel by be added into dissolution slurry (S2) crosslinking agent and with low aggregate rate into
Row prepolymerization and obtain, the MMA based polymer containing the monomer comprising MMA, noncrosslinking MMA based polymer and crosslinking.
(process (2))
It include various of monomer (M3), the polymerization initiator, friendship of MMA and crosslinking agent to addition in slurry (S) in process (2)
Join the citrate (D) that the boiling point under agent and 0.53kPa is 150 DEG C or more, obtains raw mixture.
It, can also be as needed using more than one other first other than MMA and crosslinking agent as monomer (M3)
Base alkyl acrylate and/or more than one other copolymerizable unsaturated monomer.It can be used as its that monomer (M3) uses
The illustration of its alkyl methacrylate and other copolymerizable unsaturated monomers with as noncrosslinking MMA based polymer (P)
The illustration for the aforementioned monomer (M) that the raw material of ((P1), (P2)) uses is identical, the propylene that the carbon atom number of optimizing alkyl is 3~12
Acid alkyl ester.The amount of MMA in monomer (M3) is preferably 60 mass % or more, more preferably 70~95 mass %.
As crosslinking agent contained in monomer (M3), it is not particularly limited, it is preferable to use having at least two in the molecule
The monomer of (methyl) acryloyl group.It can be mentioned, for example: ethylene glycol two (methyl) acrylate, 1,3- propylene glycol two (methyl) propylene
Acid esters, 1,3 butylene glycol two (methyl) acrylate, (1,3 butylene glycol two (methyl) acrylate), two (first of 1,4- butanediol
Base) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, two (first of diethylene glycol
Base) acrylate, triethylene glycol two (methyl) acrylate, dihydroxymethyl ethane two (methyl) acrylate, 1,1- dihydroxy first
Base propane two (methyl) acrylate, 2,2- dihydroxy methylpropane two (methyl) acrylate, trimethylolethane trimethacrylate (methyl)
Acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylol methane three (methyl) acrylate, tetra methylol first
Bis- [the 4- ((methyl) acryloyloxyethoxy) of alkane two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, 2,2-
Phenyl] propane, 2,2- bis- [4- ((methyl) acryloxy pentenyl oxygroup) phenyl] propane, bis- ((methyl) acryloyls of 1,4-
Oxygroup methyl) polyethylene glycol two (methyl) acrylate shown in hexamethylene and the following general formula (X) etc..From the sight of secondary forming property
Point sets out, and the amount of the crosslinking agent in monomer (M3) is preferably 0.5~3 mass %.
In above-mentioned formula (X), the integer that n is 4 or more, preferably 4~14, R is hydrogen atom or methyl.
It as polymerization initiator, is not particularly limited, 2,2 '-azos bis- (isobutyronitriles), 2, the 2 '-bis- (4- of azo can be enumerated
Methoxyl group -2,4- methyl pentane nitrile), 2,2 '-azos bis- (2,4- methyl pentane nitriles), acetyl group cyclohexylsulfonyl peroxidating
Object, isobutyryl peroxide, cumyl peroxyneodecanoate, di-isopropyl peroxydicarbonate, dicetyl peroxydicarbonate two
N-propyl, two myristin of peroxidating carbonic acid, dicetyl peroxydicarbonate two (2- ethoxyethyl group) ester, two (first of dicetyl peroxydicarbonate
Oxygroup isopropyl) ester and dicetyl peroxydicarbonate two (2- ethylhexyl) ester etc..
In process (2), addition chain-transferring agent and/or ultraviolet absorbing agent can according to need.As chain-transferring agent, can arrange
It lifts: the styrene dimers class such as α-methylstyrene dimer；The mercaptan such as n octylmercaptan, n-dodecyl mercaptan and benzenethiol
Class；The thioacetic acid such as thioacetic acid, ethyl thioglycolate and thioacetic acid butyl ester or its esters；β-mercaptopropionic acid, β-sulfydryl third
The β-mercaptopropionic acids such as sour methyl esters and β-mercaptopropionic acid monooctyl ester and its esters etc..Wherein, preferred benzene such as α-methylstyrene dimer
Ethylene dimerization body class.As ultraviolet absorbing agent, the benzotriazole such as 2- (2 '-hydroxyls -5 '-aminomethyl phenyl) benzotriazole can be enumerated
Class and triazines etc..
Citrate (D) is one kind of aliphatic polybasic acid esters, can be used as plasticizer and plays a role.Citrate (D)
Boiling point needs the secondary forming temperature for cast sheet of the invention or more.From the viewpoint of secondary forming property, under 0.53kPa
Boiling point is 150 DEG C or more, preferably 160 DEG C or more, more preferably 170 DEG C or more, is particularly preferably 180 DEG C or more, most preferably
It is 190 DEG C or more.It should be noted that as long as no being particularly expressly recited, then the boiling point of ester compounds is in this specification
The value obtained under the determination condition of 0.53kPa.When boiling point under 0.53kPa is less than 150 DEG C, it is possible to be waved when secondary forming
The plasticization effect that dissipates and cannot be consistent with additive amount.Furthermore, it is possible to cause foul smell etc. to secondary forming ambient enviroment
It influences.
Using the secondary forming product of cast sheet of the invention in purposes (bathtub, bathroom, the washing that be used to contact with warm water
Room and kitchen etc.) in the case where, a possibility that dissolution micro there are plasticizer.Therefore, usually it is widely used as vinyl chloride-based resin
The O-phthalics such as the DEHP (boiling point under phthalic acid two (2- ethylhexyl) ester, 0.53kPa: 386 DEG C) of plasticizer
Even if the boiling point under acid esters 0.53kPa is 150 DEG C or more, the viewpoint of the safety from user and the load to aquatic environment goes out
Hair is not also preferred.
From the viewpoint of highly-safe, small to the load of aquatic environment to user, citrate (D) is preferred
's.As citrate (D), the acetyl group that preferably can also be used in therapeutic medical pipe and bag for requiring higher safety etc.
Tributyl citrate (ATBC) etc..
In process (2), it can according to need the addition colorants such as pigment and dyestuff.
Citrate (D) also is suitable as the decentralized medium of the additives such as colorant.For example, colorant etc. can be made in advance
Additive is scattered in citrate (D) and obtains mixture, is added in slurry (S).
In process (2), it can according to need the other additives for adding more than one.As other additives, can enumerate
Diverse other resins, antioxidant, dispersing agent, filler, resin shot-like particle and the decorative patterns materials such as natural stone is granular, with
And release agent etc..
The match ratio of raw material is not particularly limited.By the total of the raw material in addition to polymerization initiator and ultraviolet absorbing agent
Amount is set as 100 mass parts.The amount of slurry (S) (preferably prepolymerization slurry (S1) or dissolution slurry (S2)) is preferably 30~98 mass
Part, more preferably 50~95 mass parts.The amount of monomer (M3) is preferably 2~70 mass parts, more preferably 5~50 mass parts.It hands over
The amount of connection agent is preferably 0.01~1.5 mass parts, more preferably 0.3~0.8 mass parts.The amount of chain-transferring agent is preferably 0~0.5
Mass parts.
When citrate (D) is very few, can not effectively obtain plasticization effect brought by adding shows effect, excessively
When, the bad orders such as glossy decline and heat-proof water albefaction decline etc. may.The amount of citrate (D) is preferably 0.1~10
Mass parts, more preferably 0.5~5 mass parts.
About the amount of polymerization initiator, relative to raw material of every 1kg in addition to polymerization initiator and ultraviolet absorbing agent
Total amount, preferably 0.05~3g.About the amount of ultraviolet absorbing agent, relative to every 1kg except polymerization initiator and ultraviolet light are inhaled
Receive the total amount of the raw material other than agent, preferably 0~2g.
(process (3))
In process (3), the raw mixture of liquid obtained in process (2) is injected into mold and is polymerize, thus
Manufacture is comprising being 150 DEG C containing the boiling point under noncrosslinking MMA based polymer (P), crosslinking MMA based polymer (C) and 0.53kPa
The cast sheet (once-forming) of the Methacrylic resin composition of above citrate (D).
Cast polymerization can be carried out by known method.It as mold, can enumerate: by strengthened glass, chrome plating or stainless
The mold that a pair of plate-shaped body and flexible vinyl chloride the system liner of steel plate etc. are constituted；And by being walked towards same direction with same speed
The opposite face of capable a pair of of endless belt and the liner structure with speed traveling identical with two endless belts positioned at its two sides edge
At mold etc..From the viewpoint of improving aggregate rate, the polymerization of raw mixture is preferably set to 40~90 DEG C of one-step solidification
With the two stages of the secondary curing of 110~130 DEG C after it.
The concentration of noncrosslinking straight-chain MMA based polymer (P) in Methacrylic resin composition is preferably 5~
40 mass %, more preferably 5~25 mass %.Methacrylic resin composition in Methacrylic resin composition
In crosslinking MMA based polymer (C) concentration be preferably 60~95 mass %, more preferably 75~95 mass %.It is crosslinked MMA system
Polymer (C) is to be copolymerized the monomer (M3) comprising MMA and crosslinking agent with the monomer (M) comprising MMA in slurry (S)
's.
It should be noted that the measuring method of the content of crosslinking MMA based polymer (C) is as described below.From methacrylic acid
Sample is acquired in based resin composition, is ground into the granular of 2~3mm, and smashed sample is used to the day of the precision with 0.1mg
It is flat to be weighed.Then, smashed sample is put into cylindrical filter paper, it is solvable by solvent extraction of chloroform with Soxhlet extractor
Ingredient will extract residue dried under vacuum 48 hours, the quality for the insoluble component that weighs with scale.Thus, it is possible to calculate crosslinking MMA
The content of based polymer (C).The content that citrate (D) can be measured by soluble ingredient, can further make soluble ingredient again
It precipitates to measure the content and weight average molecular weight (Mw) of noncrosslinking straight-chain MMA based polymer (P).
[secondary forming product]
Secondary forming product of the invention are to carry out secondary forming form to above-mentioned cast sheet of the present invention (primary molded product)
's.Bending machining and deep-draw deep processing etc., the available secondary forming product with bending section are implemented to cast sheet of the invention.
As secondary forming method, vacuum forming and the empty forming of pressure etc. can be enumerated.Cast sheet can be used into heating furnace in advance
After being heated to suitable temperature, using vacuum, compression, air, mechanical compression and their combination, cast sheet is made to follow mould
Tool, is thus processed into desired shape.Secondary forming temperature is preferably 150 DEG C or more, more preferably 180 DEG C or more.
Cast sheet of the invention includes Methacrylic resin composition, therefore has the transparency, coloring, forming
Property, the metha crylics resin such as weatherability and surface hardness originally possessed by characteristic.Cast sheet of the invention includes crosslinking
MMA based polymer (C), therefore it is able to carry out bending machining and deep-draw deep processing etc..Cast sheet of the invention further comprises as increasing
Therefore the citrate (D) that modeling agent is worked improves elongation in the state of maintaining the rigidity of plate, can have higher
Shaping processability.Therefore, by using cast sheet of the invention, the thickness in portion and coupled extension section can be bent
The uneven secondary forming product small, dimensional accuracy is high of degree.
From the viewpoint of highly-safe, small to the load of aquatic environment to user, citrate (D) is preferred
's.It is 150 DEG C or more of citrate (D) by using the boiling point under 0.53kPa, the citrate (D) when secondary forming
Being vaporized is inhibited, and can stably obtain the plasticization effect being consistent with additive amount, without worrying to secondary forming ambient enviroment
The influence for causing foul smell etc., is therefore preferred.
As discussed above, add according to the present invention it is possible to provide and can implement bending with higher dimensional accuracy
The cast sheet and its manufacturing method of work and deep-draw deep processing etc..
It should be noted that cast sheet of the invention preferably forms bending in implementation bending machining and deep-draw deep processing etc.
It is used in the case where portion, but can be used for arbitrary purposes.
Cast sheet of the invention can be preferred in the bathrooms field such as bathtub, bathroom and washroom and whole kitchen
Formed products used in the kitchens such as top plate field etc..
Cast sheet of the invention can not only be processed into high precision stretches the central portion of plate and shape along a direction
At the simple shape of bowl shape etc, additionally it is possible to be processed into reply with high precision with walking auxiliary tool and without the general of step etc.
Design (accessible) and designer's article etc., more complicated diversified shape.
Embodiment
Examples and comparative examples of the present invention are illustrated.
" weight average molecular weight (Mw) "
The measuring method of weight average molecular weight (Mw) is as described below.
Sample 5g is extracted into processing with chloroform 200ml, is filtered, methanol is added into the filtrate of collection and generates precipitating
Object.After sediment vacuum drying, 0.12g therein is dissolved in tetrahydrofuran 20ml, obtains measurement sample.As point
Sub- amount determining device, " LC-9A " manufactured using Shimadzu Seisakusho Ltd., as column, " the GPC- manufactured using Shimadzu Seisakusho Ltd.
802 ", " HSG-30 " and " HSG-50 " and " the Shodex A-806 " of Showa Denko K. K's manufacture, utilizes GPC (gel
Permeation chromatography) method carry out molecular weight measurement.
" material "
The material used is as described below.
< monomer (M1) >
MMA。
< monomer (M3): > other than crosslinking agent
MMA、
2-EHA,
N-butyl acrylate.
< monomer (M3): crosslinking agent >
1,3 butylene glycol dimethylacrylate,
Ethylene glycol dimethacrylate,
N=4 shown in above-mentioned logical formula (X) and R are polyethylene glycol dimethacrylate, the neopentyl glycol dimethyl of methyl
Acrylate.
< polymerization initiator >
2,2 '-azos bis- (isobutyronitriles),
2,2 '-azos are bis- (2,4- methyl pentane nitrile).
< chain-transferring agent >
α-methylstyrene dimer.
< ultraviolet absorbing agent >
2- (2 '-hydroxyls -5 '-aminomethyl phenyl) benzotriazole.
< pigment >
White pigment (titanium oxide).
< citrate (D) >
ATBC: citroflex A-4 (boiling point under 0.53kPa: 200 DEG C).
< citrate (D ') >
ATEC: CitroflexA-2 (boiling point under 0.53kPa: 140 DEG C).
< pigment/citrate (D) mixture >
60 mass parts of white pigment (titanium oxide) and 40 mass parts of ATBC are cooperated, are stirred using homogenizer with 5000rpm
Mixing 1 minute, obtains pigment/citrate (D) mixture of liquid.
The manufacture of [Production Example 1] prepolymerization slurry (S1-1)
It operates, is obtained containing noncrosslinking straight-chain obtained from monomer (M1) polymerization made comprising MMA as described below
The prepolymerization slurry (S1) of MMA based polymer (P1).
Into the MMA as monomer (M1), 2,2 '-azos of the addition as polymerization initiator are bis- (isobutyronitrile), while stirring
Heating, the polymerization is continued until until the weight average molecular weight (Mw) of polymer reaches about 800,000.Then it is cooled down in polymerization midway,
Additional dilution is carried out using MMA, to manufacture the prepolymerization slurry (S1-1) that viscosity is 10 pools.It should be noted that viscosity makes
It is measured with Brookfield viscometer (NDJ-5S rotational viscometer, revolving speed: 12rpm, rotor: L-type 2).
[Examples 1 to 4, comparative example 1~3]
Using the material prepared in the above described manner, according to shown in table 1-1 and table 1-2 with the raw material for being combined into preparation solution shape
Mixture.In table 1-1 and table 1-2, the unit of the use level of the raw material in addition to polymerization initiator and ultraviolet absorbing agent is
" mass parts ", the total amount of the raw material in addition to polymerization initiator and ultraviolet absorbing agent are 100 mass parts.Polymerization initiator and
The use level of ultraviolet absorbing agent is with the total amount of the raw material relative to every 1kg in addition to polymerization initiator and ultraviolet absorbing agent
Additive amount [g] indicate.
After carrying out deaeration processing to obtained raw mixture, enable its flow by a pair of of strengthened glass and soft PVC
In the mold that system liner is constituted, is heated 2 hours at 60 DEG C and make its one-step solidification.Further heat 2 hours at 120 DEG C and
Make its secondary curing, after being cooled to about 60 DEG C, taken out from mold, obtains the cast sheet of long 1250mm, width 2500mm, thickness 3mm
(primary molded product).
The heater of obtained cast sheet vacuum former is heated to 150 DEG C (secondary forming temperature conditions 1) or 180
After DEG C (secondary forming temperature condition 2), it is placed in the bucket-shaped mold (external dimensions: long 775mm, width that upper surface has opening portion
1350mm, high 700mm) on, the entire periphery of cast sheet is clamped with clip.Mold is pushed to the state, then, with true
Empty pumping goes out the air in the space between mold and cast sheet, and cast sheet is thus made to follow the interior shape of bucket-shaped mold,
The secondary forming box for upper surface with opening portion.It is cooled to about 70 DEG C with air blower, it will be secondary after cooling be hardened
Formed products are removed from mold.In above-mentioned secondary forming process, for forming when foul smell, felt based on following benchmark
Official's evaluation.Operate in the above manner, obtain external dimensions be long 775mm, width 1350mm, high 700mm box it is secondary at
Shape product.
(evaluation 1)
With the naked eye the appearance of secondary forming product obtained in each example is confirmed, is based on following benchmark evaluation bending machinings
Whether portion and coupled extension section (obtain faithful to because of apparent condition caused by uneven thickness and mold reproducibility
The formed products of mold).Determinating reference is as described below.
(determinating reference)
Foul smell > when < shapes
Zero is good: imperceptible offending foul smell.
△ has: having foul smell, but the degree not mind.
× it is smelly: foul smell makes us minding.
< formability >
Zero is good: there is no problem.
△ is thin: visual confirmation plate thickness is relatively thin.
△ is coarse: in plate surface visual confirmation to orange peel shape is coarse and fold etc..
× albefaction: onboard visual confirmation to albefaction.
× rupture: extension section is not completely stretched and is broken.
× figuration: non-figuration is mold shape.
The overall merit > of < formability
A (good): mold reproducibility is good, not because of bad order caused by uneven thickness.
B (qualifying): mold reproducibility is good, but slightly because of bad order caused by uneven thickness.
C (bad): mold reproducibility is poor, bad order caused by having because of uneven thickness.
Show the results of the evaluation table 2-1 and table 2-2.
In Examples 1 to 4, manufacture comprising containing noncrosslinking MMA based polymer (P), crosslinking MMA based polymer (C) and
The cast sheet of the Methacrylic resin composition for the citrate (D) that boiling point under 0.53kPa is 150 DEG C or more.These
In embodiment, available imperceptible forming when foul smell, bending machining portion and extension section because of uneven thickness caused by
There is no/or secondary forming product few, that dimensional accuracy is high, mold reproducibility is high for bad order.
It is not added in the comparative example 1,3 of citrate (D), has obtained bending machining portion or extension section exists because of uneven thickness
The insufficient secondary forming product of caused bad order, the aesthetics without mold reproducibility, appearance.The boiling under 0.53kPa is used
In the comparative example 2 of citrate (D ') o'clock less than 150 DEG C, although not observed because of thickness not in bending machining portion and extension section
Bad order caused by, but determines that foul smell when forming.
(evaluation 2)
The representative sample of overall merit A, B, C as formability, to obtained in embodiment 2, comparative example 1, comparative example 3
The uneven thickness of secondary forming product (forming temperature: 180 DEG C) is evaluated.
It selects to curve it processing department at one in the bottom four corners portion of obtained secondary forming product and extension section is cut
It is disconnected, obtain segment.Observe that (secondary forming product good for appearance are for the region of bad order in obtained segment
Corresponding region) in, 10 positions are arbitrarily selected along the depth direction of secondary forming product, are measured using micrometer each
The thickness of position.It is calculated with adjacent to each other 2 points of the thickness absolute value of the difference to locate and amounts to 9 values, find out theirs
Average value.The measurement result of the average value of thickness difference is as described below.
Embodiment 2 (the overall merit A of formability): 0.016mm,
Comparative example 1 (the overall merit B of formability): 0.021mm,
Comparative example 3 (the overall merit C of formability): 0.024mm.
From the above results, the embodiment 2 of no bad order is compared with the comparative example 1,3 for having bad order, and thickness is not
It is small.
[table 2-1]
[table 2-2]
The present invention is not limited to the above embodiments and embodiment, can be appropriate without departing from the spirit and scope of the invention
Design alteration.
This application claims preferential based on Japanese publication Patent 2017-053048 proposed by March 17th, 2017
Power, the entire disclosure is incorporated in this specification.
Claims (5)
1. a kind of cast sheet, it includes Methacrylic resin composition, the Methacrylic resin composition contains
Under noncrosslinking methyl methacrylate based polymer (P), crosslinked methyl methacrylate based polymer (C) and 0.53kPa
The citrate (D) that boiling point is 150 DEG C or more.
2. a kind of manufacturing method of cast sheet described in claim 1, wherein
Prepare containing the monomer (M) comprising methyl methacrylate and noncrosslinking methyl methacrylate based polymer (P)
Slurry (S),
It is to the boiling point being added in slurry (S) under the monomer (M3) and 0.53kPa comprising methyl methacrylate and crosslinking agent
150 DEG C or more of citrate (D),
Obtained raw mixture is subjected to cast polymerization.
3. the manufacturing method of cast sheet according to claim 2, wherein slurry (S) is containing making comprising methacrylic acid
The prepolymerization slurry (S1) of noncrosslinking methyl methacrylate based polymer (P1) obtained from monomer (M1) polymerization of methyl esters.
4. the manufacturing method of cast sheet according to claim 2, wherein slurry (S) is to make noncrosslinking methacrylic acid
Dissolution slurry (S2) obtained from methyl esters based polymer (P2) is dissolved in the monomer comprising methyl methacrylate (M2).
5. a kind of secondary forming product, are made of cast sheet described in claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017053048 | 2017-03-17 | ||
| JP2017-053048 | 2017-03-17 | ||
| PCT/JP2018/010052 WO2018168954A1 (en) | 2017-03-17 | 2018-03-14 | Cast sheet, method for manufacturing same, and secondary molded article |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110418818A true CN110418818A (en) | 2019-11-05 |
Family
ID=63523113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880018448.2A Pending CN110418818A (en) | 2017-03-17 | 2018-03-14 | Cast sheet and its manufacturing method and secondary forming product |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPWO2018168954A1 (en) |
| CN (1) | CN110418818A (en) |
| WO (1) | WO2018168954A1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2018168954A1 (en) | 2018-09-20 |
| JPWO2018168954A1 (en) | 2020-01-16 |
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