U.S. patent application number 15/685882 was filed with the patent office on 2018-03-01 for lamination-shaped fired body, method for producing lamination-shaped fired body, and kit for producing lamination-shaped fired body.
The applicant listed for this patent is Noritake Co., Limited. Invention is credited to Akihiro Okashimo, Daishi Yoshikawa.
Application Number | 20180057411 15/685882 |
Document ID | / |
Family ID | 61166850 |
Filed Date | 2018-03-01 |
United States Patent
Application |
20180057411 |
Kind Code |
A1 |
Yoshikawa; Daishi ; et
al. |
March 1, 2018 |
LAMINATION-SHAPED FIRED BODY, METHOD FOR PRODUCING
LAMINATION-SHAPED FIRED BODY, AND KIT FOR PRODUCING
LAMINATION-SHAPED FIRED BODY
Abstract
The present invention provides a method for producing a
lamination-shaped fired body. This production method includes a
shaping step (S10) of shaping a lamination-shaped article by using
a lamination shaping powder that contains non-hydrating reaction
raw material particles, an impregnation step (S20) of impregnating
the lamination-shaped article with a coupling liquid that contains
a coupling agent, and a firing step (S30) of firing the
lamination-shaped article so as to obtain a lamination-shaped fired
body, implemented following the impregnation step.
Inventors: |
Yoshikawa; Daishi;
(Nisshin-shi, JP) ; Okashimo; Akihiro;
(Nagakute-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Noritake Co., Limited |
Nagoya-shi |
|
JP |
|
|
Family ID: |
61166850 |
Appl. No.: |
15/685882 |
Filed: |
August 24, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C04B 2235/3232 20130101;
C04B 35/64 20130101; C04B 2235/6567 20130101; C04B 2235/616
20130101; C04B 35/46 20130101; C04B 35/6325 20130101; C04B 35/63416
20130101; C04B 2235/3244 20130101; C04B 35/111 20130101; C04B
35/486 20130101; C04B 35/14 20130101; C04B 2235/5436 20130101; C04B
2235/96 20130101; C04B 2235/48 20130101; C04B 35/632 20130101; C04B
35/48 20130101; C04B 2235/483 20130101; C04B 2235/3217 20130101;
C04B 2235/606 20130101; C04B 2235/3418 20130101; C04B 2235/602
20130101; C04B 2235/6562 20130101; C04B 35/10 20130101; C04B 35/636
20130101; C04B 2235/85 20130101 |
International
Class: |
C04B 35/48 20060101
C04B035/48; C04B 35/10 20060101 C04B035/10; C04B 35/632 20060101
C04B035/632; C04B 35/64 20060101 C04B035/64; C04B 35/634 20060101
C04B035/634 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 24, 2016 |
JP |
2016-163571 |
Claims
1. A method for producing a lamination-shaped fired body, the
method comprising: a shaping step of shaping a lamination-shaped
article by using a lamination shaping powder that contains
non-hydrating reaction raw material particles; an impregnation step
of impregnating the lamination-shaped article with a coupling
liquid that contains a coupling agent; and a firing step of firing
the lamination-shaped article so as to obtain a lamination-shaped
fired body, implemented following the impregnation step.
2. The method for producing a lamination-shaped fired body
according to claim 1, wherein the coupling agent contains at least
one element selected from the group consisting of Si, Ti, Al and
Zr.
3. The method for producing a lamination-shaped fired body
according to claim 1, wherein the non-hydrating reaction raw
material particles are constituted mainly from a metal containing
at least one element selected from the group consisting of Al, Zr,
Ti, Zn, Ni and Fe or an alloy thereof.
4. The method for producing a lamination-shaped fired body
according to claim 1, wherein the non-hydrating reaction raw
material particles are constituted mainly from an oxide containing
at least one element selected from the group consisting of Al, Zr,
Ti, Zn, Ni, Fe and Si.
5. The method for producing a lamination-shaped fired body
according to claim 1, wherein the lamination shaping powder further
contains water-soluble adhesive particles, and the shaping step
includes processing of supplying a water-containing shaping liquid
to a deposit of the lamination shaping powder so as to form a
hardened layer.
6. The method for producing a lamination-shaped fired body
according to claim 5, wherein the water-soluble adhesive particles
comprise poly(vinyl alcohol) or a derivative thereof.
7. A kit for producing a lamination-shaped fired body, the kit
being used to produce a lamination-shaped fired body obtained by
firing a lamination-shaped article and comprising: a lamination
shaping powder that contains non-hydrating reaction raw material
particles, and a coupling liquid which contains a coupling agent
and which is impregnated in an unfired lamination-shaped article
that is shaped using the lamination shaping powder.
8. The kit for producing a lamination-shaped fired body according
to claim 7, wherein the coupling agent contains at least one
element selected from the group consisting of Si, Ti, Al and
Zr.
9. The kit for producing a lamination-shaped fired body according
to claim 7, wherein the non-hydrating reaction raw material
particles are constituted mainly from a metal containing at least
one element selected from the group consisting of Al, Zr, Ti, Zn,
Ni and Fe or an alloy thereof.
10. The kit for producing a lamination-shaped fired body according
to claim 7, wherein the non-hydrating reaction raw material
particles are constituted mainly from an oxide containing at least
one element selected from the group consisting of Al, Zr, Ti, Zn,
Ni, Fe and Si.
11. The kit for producing a lamination-shaped fired body according
to claim 7, wherein the lamination shaping powder further contains
water-soluble adhesive particles.
12. The kit for producing a lamination-shaped fired body according
to claim 11, wherein the water-soluble adhesive particles comprise
poly(vinyl alcohol) or a derivative thereof.
13. A lamination-shaped fired body formed by a multiplicity of
non-hydrating reaction raw material particles binding to each
other, wherein the non-hydrating reaction raw material particles
contain at least one element selected from the group consisting of
Al, Zr, Ti, Zn, Ni, Fe and Si, and an oxide containing at least one
element selected from the group consisting of Si, Ti, Al and Zr,
other than elements contained in the non-hydrating reaction raw
material particles, is present at grain boundaries between
non-hydrating reaction raw material particles.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
[0001] The present invention relates to a lamination-shaped fired
body, a method for producing a lamination-shaped fired body, and a
kit for producing a lamination-shaped fired body.
[0002] The present application claims priority under 35 U.S.C.
.sctn.119 to Japanese Patent Application No. 2016-163571, which was
filed on 24 Aug. 2016, and the entire contents of that application
are incorporated by reference in the present specification.
2. Description of the Related Art
[0003] In the past, additive manufacturing (also known as
three-dimensional manufacturing) has been known, in which a shaped
article having a desired three-dimensional shape is shaped by
binding a powder material by means of a binder and forming a
solidified powder layer having a prescribed cross sectional shape.
Due to ease of handling, this additive manufacturing is widely
carried out for manufacturing resin products obtained using resin
materials. However, additive manufacturing of powder materials
(powder lamination shaping) is also widely used for powder
materials comprising ceramic materials, for which precision
processing following shaping is difficult. Japanese Patent
Application Publication No. 2015-226935 is cited as an example of a
technical document relating to lamination shaping of this type of
ceramic material.
SUMMARY OF THE INVENTION
[0004] Japanese Patent Application Publication No. 2015-226935
discloses shaping a lamination-shaped article (a ceramic casting
core in this case) using a lamination shaping powder that contains
a ceramic powder and a binder, and then firing the
lamination-shaped article at a high temperature. This document
indicates that by being constituted in this way, it is possible to
obtain a lamination-shaped article which has adequate core strength
and other associated fired physical and chemical properties.
However, even if such a constitution is used, the mechanical
strength of a lamination-shaped article is insufficient to satisfy
levels required in recent years, and there is still room for
improvement.
[0005] With these circumstances in mind, the main purpose of the
present invention is to provide a method for producing a
lamination-shaped fired body by which the mechanical strength of a
lamination-shaped article can be improved. A related purpose of the
present invention is to provide a kit for producing a
lamination-shaped fired body able to contribute to such an increase
in strength.
[0006] In order to achieve the purposes mentioned above, the
present invention provides a method for producing a
lamination-shaped fired body. The production method disclosed here
includes: a shaping step of shaping a lamination-shaped article by
using a lamination shaping powder that contains non-hydrating
reaction raw material particles: an impregnation step of
impregnating the lamination-shaped article with a coupling liquid
that contains a coupling agent; and a firing step of firing the
lamination-shaped article so as to obtain a lamination-shaped fired
body, implemented following the impregnation step.
[0007] By impregnating a lamination-shaped article with a coupling
liquid and then firing in this way, the mechanical strength of a
lamination-shaped fired body can be greatly improved.
[0008] In a preferred aspect of the invention disclosed here, the
coupling agent contains at least one element selected from the
group consisting of Si, Ti, Al and Zr. By using such a coupling
agent, greater mechanical strength can be achieved.
[0009] In a preferred aspect of the invention disclosed here, the
non-hydrating reaction raw material particles are constituted
mainly from a metal containing at least one element selected from
the group consisting of Al, Zr, Ti, Zn, Ni and Fe or an alloy
thereof. By using these non-hydrating reaction raw material
particles in combination with the coupling agent, a
lamination-shaped fired body having greater strength can be
obtained.
[0010] In a preferred aspect of the invention disclosed here, the
non-hydrating reaction raw material particles are constituted
mainly from an oxide containing at least one element selected from
the group consisting of Al, Zr, Ti, Zn, Ni, Fe and Si. By using
these non-hydrating reaction raw material particles in combination
with the coupling agent, a lamination-shaped fired body having
greater strength can be obtained.
[0011] In a preferred aspect of the invention disclosed here, the
lamination shaping powder further contains water-soluble adhesive
particles. In addition, the step of shaping the lamination-shaped
article includes processing of supplying a water-containing shaping
liquid to a deposit of the lamination shaping powder so as to form
a hardened layer. The advantageous effect of the present invention
can be more advantageously exhibited in a method for producing a
lamination-shaped fired body that includes a shaping step that uses
a shaping liquid containing water-soluble adhesive particles and
water in this way.
[0012] In a preferred aspect of the invention disclosed here, the
water-soluble adhesive particles comprise poly(vinyl alcohol) or a
derivative thereof. By using such water-soluble adhesive particles,
the production method disclosed here can be advantageously carried
out.
[0013] According to this specification, a kit which is used to
produce a lamination-shaped fired body obtained by firing a
lamination-shaped article is also provided. This production kit
includes a lamination shaping powder that contains non-hydrating
reaction raw material particles, and a coupling liquid which
contains a coupling agent and which is impregnated in an unfired
lamination-shaped article that is shaped using the lamination
shaping powder. By using such a production kit, it is possible to
produce a high quality lamination-shaped fired body having superior
mechanical strength to the prior art.
[0014] The coupling agent may contain at least one element selected
from the group consisting of Si, Ti, Al and Zr. The non-hydrating
reaction raw material particles may be constituted mainly from a
metal containing at least one element selected from the group
consisting of Al, Zr, Ti, Zn, Ni and Fe or an alloy thereof. The
non-hydrating reaction raw material particles may be constituted
mainly from an oxide containing at least one element selected from
the group consisting of Al, Zr, Ti, Zn, Ni, Fe and Si. The
lamination shaping powder may further contain water-soluble
adhesive particles. The water-soluble adhesive particles comprise
poly(vinyl alcohol) or a derivative thereof.
[0015] According to this specification, a lamination-shaped fired
body is also provided. This lamination-shaped fired body is formed
by a multiplicity of non-hydrating reaction raw material particles
binding to each other. The non-hydrating reaction raw material
particles contain at least one element selected from the group
consisting of Al, Zr, Ti, Zn, Ni, Fe and Si. An oxide containing at
least one element selected from the group consisting of Si, Ti, Al
and Zr, other than elements contained in the non-hydrating reaction
raw material particles, is present at grain boundaries between
non-hydrating reaction raw material particles. This
lamination-shaped fired body can achieve excellent mechanical
strength.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 is a diagram that shows a production flow of a
lamination-shaped fired body according to one embodiment.
DETAILED DESCRIPTION OF THE INVENTION
[0017] Preferred embodiments of the present invention will now be
explained. Moreover, matters which are essential for carrying out
the invention and which are matters other than those explicitly
mentioned in the present specification are matters that a person
skilled in the art could understand to be matters of design on the
basis of the prior art in this technical field. The present
invention can be carried out on the basis of the matters disclosed
in the present specification and common general technical knowledge
in this technical field.
[0018] The lamination shaping powder disclosed here, which contains
non-hydrating reaction raw material particles, forms a hardened
layer (a solidified powder layer) having a prescribed cross
sectional shape as a result of the powder being bound by a binder,
and by forming this hardened layer while sequentially laminating,
the lamination shaping powder can be used in a variety of types of
additive manufacturing in which lamination-shaped articles having
prescribed three-dimensional shapes are shaped. It is particularly
preferable to use the lamination shaping powder in additive
manufacturing involving the use of a powder fixing lamination
method for forming a lamination-shaped article by depositing a
lamination shaping powder in the form of a thin layer, forming a
hardened layer by mixing a water-containing shaping liquid with a
prescribed region of the deposit and repeatedly forming hardened
layers. The present invention will now be explained in greater
detail using an example of a case in which additive manufacturing
involving the use of mainly a powder fixing lamination method is
carried out, but the scope of the present invention is not limited
thereto. For example, the present invention can also be used in an
optical shaping technique in which a lamination-shaped article is
shaped by hardening a slurry, which is obtained by mixing
non-hydrating reaction raw material particles with a photocurable
resin, through irradiation with light.
[0019] A procedure for producing a lamination-shaped fired body
will now be explained with reference to FIG. 1. FIG. 1 is a flow
diagram showing this production process. The production method of
this embodiment has a shaping step (step S10), an impregnation step
(step S20) and a firing step (step S30).
[0020] Here, the shaping step of step S10 comprises shaping a
lamination-shaped article using a lamination shaping powder that
contains non-hydrating reaction raw material particles. The
impregnation step of step S20 comprises impregnating the
lamination-shaped article, which is shaped in the shaping step,
with a coupling liquid that contains a coupling agent. The firing
step of step S30 comprises firing the lamination-shaped article so
as to obtain a lamination-shaped fired body. By impregnating the
lamination-shaped article with the coupling liquid and then firing
in this way, the mechanical strength of the lamination-shaped fired
body can be greatly improved. These steps will now be explained in
greater detail.
[0021] Molding Step
[0022] In the shaping step of step S10, a lamination-shaped article
is shaped using a lamination shaping powder that contains
non-hydrating reaction raw material particles. In this embodiment,
a lamination shaping powder that contains non-hydrating reaction
raw material particles and water-soluble adhesive particles is
prepared, and a lamination-shaped article is shaped by means of a
powder fixing lamination method using this lamination shaping
powder. Here, the term "non-hydrating reaction raw material
particles" in the present specification means a substance which,
when the particles come into contact with water, does not undergo a
hydration reaction (typically generation of a hydrate or generation
of a hydroxide) or, if the substance does undergo a hydration
reaction, the hydration reaction is limited to only a microscopic
region of the surface of the particles, with the majority of the
particles substantially not reacting with water. Therefore, a case
in which, for example, a trace quantity (for example, 0.1 moles or
less, preferably 0.01 moles or less, and more preferably 0.001
moles or less) locally reacts with 1 mole of non-hydrating reaction
raw material particles at particle surfaces can be encompassed by
the concept of non-hydrating reaction raw material particles
mentioned here. Gypsum and cement can be given as typical examples
of substances that undergo hydration reactions. The non-hydrating
reaction raw material particles are a component that constitutes
the base material of the lamination-shaped article that is an
object to be shaped.
[0023] The constituent material and shape of the non-hydrating
reaction raw material particles are not particularly limited. For
example, the non-hydrating reaction raw material particles may be
inorganic particles, organic particles or organic-inorganic
composite particles. The non-hydrating reaction raw material
particles are preferably inorganic particles and, of these, are
preferably particles comprising a metal or metalloid compound. For
example, non-hydrating reaction raw material particles constituted
mainly from an oxide, nitride, carbide, or the like, containing
elements belonging to groups 4 to 14 of the periodic table can be
advantageously used. Of these, non-hydrating reaction raw material
particles constituted mainly from an oxide (a ceramic), nitride,
carbide, or the like, containing metal elements or metalloid
elements selected from among Al, Zr. Ti, Zn, Ni, Fe and Si are
preferred. Alternatively, it is possible to use non-hydrating
reaction raw material particles constituted mainly from a metal
containing elements belonging to groups 4 to 13 of the periodic
table or an alloy of these elements. Of these, non-hydrating
reaction raw material particles constituted mainly from a metal
containing metal elements selected from among Al, Zr, Ti, Zn, Ni
and Fe or an alloy of these elements are preferred.
[0024] Specific examples include non-hydrating reaction raw
material particles constituted mainly from oxide particles such as
aluminum oxide (for example, alumina) particles, zirconium oxide
(for example, zirconia) particles, titanium oxide (for example,
titania) particles, silicon oxide (for example, silica) particles,
zinc oxide particles, iron oxide particles, nickel oxide particles,
cerium oxide (for example, ceria) particles, magnesium oxide (for
example, magnesia) particles, chromium oxide particles, manganese
dioxide particles, barium titanate particles, calcium carbonate
particles and barium carbonate particles, metal particles such as
aluminum particles, nickel particles and iron particles: nitride
particles such as silicon nitride particles and boron nitride
particles; and carbide particles such as silicon carbide particles
and boron carbide particles. It is possible to use one type of
non-hydrating reaction raw material particles in isolation, or a
combination of two or more types thereof. Of these, alumina
particles, zirconia particles, titania particles, silica particles,
zinc oxide particles, barium titanate particles, aluminum
particles, nickel particles and iron particles are preferred from
the perspective of being able to form a highly strong
three-dimensional shaped article. Of these, alumina particles,
zirconia particles, titania particles and silica particles are more
preferred, and alumina particles are particularly preferred.
[0025] Moreover, in the present specification, the expression
"constituted mainly from A" with respect to the composition of the
non-hydrating reaction raw material particles means that the
proportion of A (the purity of A) in the non-hydrating reaction raw
material particles is 90% or more (preferably 95% or more, more
preferably 97% or more and further preferably 98% or more, for
example 99% or more) in terms of mass.
[0026] The shape (external shape) of the non-hydrating reaction raw
material particles may be spherical or non-spherical. From
perspectives such as mechanical strength and ease of production,
roughly spherical non-hydrating reaction raw material particles can
be advantageously used. The average particle diameter of the
non-hydrating reaction raw material particles is not particularly
limited, but can be, for example, not less than 5 .mu.m and not
more than 60 .mu.m. If the average particle diameter of the
non-hydrating reaction raw material particles is too low, the
lamination shaping powder becomes unlikely to flow, meaning that
moldability may deteriorate when the powder is packed in the form
of a thin layer during shaping. From perspectives such as
moldability, the average particle diameter of the non-hydrating
reaction raw material particles is preferably not less than 10
.mu.m, more preferably not less than 20 .mu.m, and particularly
preferably not less than 30 .mu.m (for example, not less than 40
.mu.m). In addition, the average particle diameter of the
non-hydrating reaction raw material particles is not more than
approximately 60 .mu.m. If the average particle diameter of the
non-hydrating reaction raw material particles is too high, the
powder readily flows after being packed in the form of a thin layer
during shaping, meaning that layers in the lamination-shaped
article may undergo lamination slipping. From perspectives such as
suppressing lamination slipping, the average particle diameter of
the non-hydrating reaction raw material particles is preferably not
more than 55 .mu.m, more preferably not more than 50 .mu.m, and
particularly preferably not more than 45 .mu.m. For example,
non-hydrating reaction raw material particles in which the average
particle diameter is such that 10 .mu.m.ltoreq.X.ltoreq.50 .mu.m
(and typically 30 .mu.m.ltoreq.X.ltoreq.50 .mu.m) are preferred
from the perspective of achieving moldability while suppressing
lamination slipping.
[0027] Moreover, the term "average particle diameter" in the
present specification, unless explicitly stated otherwise, means
the particle diameter at a cumulative value of 50% in a particle
size distribution measured using a laser scattering/diffraction
type particle size distribution measurement apparatus, that is, the
50% volume average particle diameter (D50 diameter). More
specifically, this average particle diameter is the 50% volume
average particle diameter measured by means of a dry method using a
laser scattering/diffraction type particle size distribution
measurement apparatus, without dispersing particles by means of
compressed air.
[0028] The content of non-hydrating reaction raw material particles
in the lamination shaping powder is not particularly limited. The
content of non-hydrating reaction raw material particles is
generally not less than 60 parts by mass relative to a total of 100
parts by mass of the lamination shaping powder, and from
perspectives such as improving mechanical strength, is preferably
not less than 65 parts by mass, more preferably not less than 75
parts by mass, for example not less than 80 parts by mass, and is
typically not less than 85 parts by mass, for example not less than
90 parts by mass. The upper limit for the content of the
non-hydrating reaction raw material particles is not particularly
limited, but is preferably not more than 99 parts by mass, and more
preferably not more than 98 parts by mass, for example not more
than 96 parts by mass. If the content of non-hydrating reaction raw
material particles falls within a range such as that mentioned
above, the advantageous effect of the present invention can be
exhibited at a significantly higher level.
[0029] The lamination shaping powder disclosed here contains
water-soluble adhesive particles in addition to the non-hydrating
reaction raw material particles mentioned above. In the present
specification, the term "water-soluble adhesive particles" means
that when 2 parts by mass of adhesive particles are added to 100
parts by mass of water having a temperature of 90.degree. C. and
stirred for 4 hours, all or some of the adhesive particles
dissolve, and the aqueous solution in which the adhesive particles
are dissolved has a higher viscosity than water. In a preferred
aspect, in cases where the water is deemed to have a viscosity of A
(mPas), the viscosity of an aqueous solution in which the adhesive
particles are dissolved has a viscosity that is more than
1.2.times.A (preferably 1.5.times.A, and more preferably
2.0.times.A). The water-soluble adhesive particles are a component
which, when mixed with a water-containing shaping liquid, dissolve
in the water and bind non-hydrating reaction raw material particles
to each other.
[0030] The constituent material and shape of the water-soluble
adhesive particles are not particularly limited. For example,
water-soluble adhesive particles constituted mainly from
thermoplastic resins, thermosetting resins and polysaccharides can
be advantageously used.
[0031] Preferred examples of thermoplastic resins include vinyl
alcohol-based resins, isobutylene-based resins, polyamide-based
resins and polyester-based resins. Vinyl alcohol-based resins are
typically resins containing vinyl alcohol units as primary
repeating units (PVA resins). In such resins, the ratio of the
number of moles of vinyl alcohol units relative to the number of
moles of all repeating units is generally not less than 50% (for
example, 50% to 90%), and is preferably not less than 65%, and more
preferably not less than 75%, for example not less than 85%. It is
possible for substantially all of the repeating units to be
constituted from vinyl alcohol units. In PVA resins, repeating
units other than vinyl alcohol units are not particularly limited,
and may include, for example, vinyl acetate units. Anion-modified
and cation-modified PVA resins, such as carboxyl group-modified PVA
resins, sulfonic acid group-modified PVA resins and phosphoric acid
group-modified PVA resins, and modified PVA resins obtained by
copolymerizing ethylene, vinyl ethers having long chain alkyl
groups, vinyl esters, (meth)acrylamide, .alpha.-olefins, and the
like, may be used. The degree of polymerization of the PVA is not
particularly limited, but may be, for example, 100 to 5000 (and
preferably 500 to 3000). An isobutylene-based resin may be a
homopolymer of isobutylene or a copolymer of isobutylene and
another monomer (an isobutylene copolymer). In the case of
isobutylene copolymers, other monomers to be copolymerized with
isobutylene are not particularly limited. For example, it is
possible to use a monomer having an ethylenic double bond. Examples
of monomers having ethylenic double bonds include ethylenically
unsaturated carboxylic acids such as maleic acid (anhydride),
acrylic acid, methacrylic acid, phthalic acid (anhydride) and
itaconic acid (anhydride). Chemically modified isobutylene
copolymers may be used. The molecular weight of an isobutylene
copolymer is not particularly limited, but may be, for example,
3.times.10.sup.3 to 2.times.10.sup.5 (and preferably
5.times.10.sup.3 to 1.7.times.10.sup.5). Examples of
polyamide-based resins include water-soluble nylon resins obtained
by chemically modifying nylon resins such as polycaproamide
(nylon-6). Examples of polyester-based resins include water-soluble
polyesters obtained by introducing hydrophilic group-containing
components as copolymer components in polyesters. Of these,
thermoplastic resins, vinyl alcohol-based resins and
isobutylene-based resins can be advantageously used from the
perspective of adhesive strength.
[0032] Preferred examples of thermosetting resins include
melamine-based resins. A melamine resin may be a melamine resin
obtained by means of a polymerization reaction between melamine and
an aldehyde, but may also be a copolymer resin of a monomer used to
form a melamine resin (or an initial polymer thereof) and another
monomer (or an initial polymer thereof). In the case of a melamine
resin, the type of aldehyde to be polymerized with melamine is not
particularly limited. For example, a melamine resin obtained by
means of a polymerization reaction between melamine and
formaldehyde can be advantageously used.
[0033] Preferred examples of polysaccharides include cellulose
derivatives such as hydroxypropylmethyl cellulose,
hydroxyethylmethyl cellulose, hydroxyethyl cellulose, hydroxypropyl
cellulose, methyl cellulose, ethyl cellulose, ethylhydroxyethyl
cellulose and carboxymethyl cellulose, and natural polymeric
compounds such as gum Arabic, xanthan gum, curdlan, starch,
dextrin, glucomannan, agarose, carrageenan, guar gum, locust bean
gum, gum tragacanth, quince seed gum, pullulan, agar and konjak
mannan. Of these, hydroxypropylmethyl cellulose, hydroxyethylmethyl
cellulose, methyl cellulose, gum Arabic and xanthan gum can be
advantageously used from perspectives such as adhesive
properties.
[0034] Examples of water-soluble adhesive particles able to be
contained in the lamination shaping powder disclosed here include
water-soluble adhesive particles constituted mainly from
polyethylene glycol, partially neutralized sodium polyacrylate,
polyvinylpyrrolidone, polyvinylpyrrolidone copolymers, sodium
polyacrylate, sodium polyacrylate copolymers, sodium alginate,
sucrose, dextrose, fructose, lactose, gelatin, and the like. It is
possible to use one type of water-soluble adhesive particles
mentioned above in isolation, or a combination of two or more types
thereof.
[0035] Moreover, in the present specification, the expression
"constituted mainly from A" with respect to the composition of the
water-soluble adhesive particles means that the proportion of A
(the purity of A) in the water-soluble adhesive particles is 90% or
more (preferably 95% or more, more preferably 97% or more, and
further preferably 98% or more, for example 99% or more) in terms
of mass.
[0036] The average particle diameter of the water-soluble adhesive
particles is not particularly limited, but is generally not less
than 0.1 .mu.m, and preferably not less than 1 .mu.m. A suitable
upper limit for the average particle diameter of the water-soluble
adhesive particles is not more than approximately 250 .mu.m, and
preferably not more than 200 .mu.m.
[0037] The content of water-soluble adhesive particles in the
lamination shaping powder is not particularly limited. The content
of water-soluble adhesive particles is generally not less than 1
part by mass relative to a total of 100 parts by mass of the
lamination shaping powder, and from perspectives such as improving
mechanical strength, is preferably not less than 2 parts by mass,
such as not less than 4 parts by mass, and is typically not less
than 8 parts by mass. The upper limit for the content of the
water-soluble adhesive particles is not particularly limited, but
is, for example, not more than 40 parts by mass, and from
perspectives such as improving mechanical strength, is preferably
not more than 35 parts by mass, for example not more than 30 parts
by mass, for example not more than 20 parts by mass, and is
typically not more than 15 parts by mass, for example not more than
10 parts by mass.
[0038] In the invention disclosed here, the water-soluble adhesive
particles and non-hydrating reaction raw material particles may be
present as independent particles without being bonded to each
other. By causing the water-soluble adhesive particles and
non-hydrating reaction raw material particles to be present as
independent particles in this way, a desired lamination shaping
powder can be easily obtained. Alternatively, water-soluble
adhesive particles may be attached to the surface of non-hydrating
reaction raw material particles. That is, some or all of the
non-hydrating reaction raw material particles may be coated with
water-soluble adhesive particles. By constituting in this way, a
desired quantity of water-soluble adhesive particles are reliably
present between non-hydrating reaction raw material particles,
meaning that water in which water-soluble adhesive particles are
dissolved can efficiently pass between non-hydrating reaction raw
material particles. Therefore, a lamination-shaped article strength
improvement effect can be effectively achieved.
[0039] The lamination shaping powder disclosed here may, if
necessary, further contain publicly known additives able to be used
in three-dimensional shaping powders, such as dispersing agents,
thickening agents and printing aids, as long as the advantageous
effect of the present invention is not impaired. The content of
such additives should be set as appropriate according to the
purpose of the additive, and detailed explanations are omitted as
this content does not characterize the present invention.
[0040] The method for preparing the lamination shaping powder is
not particularly limited. For example, components to be contained
in the lamination shaping powder may be mixed using a well-known
mixing method, such as a PolyMix. Modes for mixing these components
are not particularly limited, and it is possible to, for example,
mix all of the components at once or mix the components in an
appropriately specified order.
[0041] The lamination shaping powder disclosed here is typically
used to shape a lamination-shaped article in a mode in which the
lamination shaping powder is mixed with a water-containing shaping
liquid.
[0042] A solvent used in the shaping liquid should be a
water-containing solvent. Pure water, ultrapure water, ion
exchanged water (deionized water), distilled water, and the like,
can be advantageously used as the solvent. The shaping liquid
disclosed here may, if necessary, further contain an organic
solvent (a lower alcohol, a lower ketone, or the like) able to be
homogeneously mixed with water. In general, it is preferable for
not less than 40 vol. %, and more preferably not less than 50 vol.
% (typically, 50 to 100 vol. %), of the solvent contained in the
shaping liquid to be water. This type of shaping liquid can be
mixed at a proportion of, for example, 20 to 80 parts by mass
(typically 40 to 60 parts by mass) relative to 100 parts by mass of
a three-dimensional shaping powder when carrying out shaping.
[0043] The shaping liquid disclosed here may, if necessary, further
contain publicly known additives able to be used in shaping
liquids, such as dyes, organic pigments, inorganic pigments,
wetting agents and flow rate-increasing agents, as long as the
advantageous effect of the present invention is not impaired. The
content of such additives should be set as appropriate according to
the purpose of the additive, and detailed explanations are omitted
as this content does not characterize the present invention.
[0044] The method for shaping the lamination-shaped article using
the lamination shaping powder is not particularly limited. For
example, the lamination-shaped article can be shaped by forming a
layer of the lamination shaping powder and then supplying a
water-containing shaping liquid to a prescribed region of the
layer. This shaping may be carried out using a 3D printer that
shapes a three-dimensional body on the basis of three-dimensional
data corresponding to a lamination-shaped article to be shaped.
This type of 3D printer may have inkjets that apply droplets of the
water-containing shaping liquid and a platen on which the
lamination shaping powder is disposed.
[0045] The lamination-shaped article is then shaped by repeating
procedures 1 to 3 below so as to successively laminate solid
layered articles.
Procedure 1: the lamination shaping powder is packed (deposited) in
the form of a layer on the platen at a thickness corresponding to
the thickness of a layer of the lamination-shaped article to be
shaped (for example, 0.01 to 0.3 mm). Procedure 2: droplets of the
water-containing shaping liquid are applied from the inkjets to
that part of the lamination shaping powder (deposit) packed in the
form of a layer that is to be hardened (that is, a part
corresponding to a portion of the lamination-shaped article to be
shaped). Next, a hardened layer (a solid layered article) is formed
by dissolving water-soluble adhesive particles contained in the
applied droplets and bonding non-hydrating reaction raw material
particles to each other. Procedure 3: the platen is lowered
vertically by an amount corresponding to the thickness of a layer
in the lamination-shaped article.
[0046] Next, shaping of the lamination-shaped article is completed
by finally removing un-hardened lamination shaping powder. This
lamination-shaped article is formed by a multiplicity of
non-hydrating reaction raw material particles being bonded to each
other by dissolved water-soluble adhesive particles, and may have a
porous structure. Following the shaping, the obtained
lamination-shaped article may be allowed to dry naturally. The
drying time is not particularly limited, but is generally 1.5 to 24
hours, and preferably 15 to 20 hours.
[0047] Impregnation Step
[0048] In the impregnation step of step S20, the lamination-shaped
article shaped in the shaping step (typically gaps between
non-hydrating reaction raw material particles that constitute the
lamination-shaped article) is impregnated with a coupling liquid
that contains a coupling agent.
[0049] The coupling agent contained in the coupling liquid can be a
compound that contains a metal element (This is a concept that
encompasses metalloid elements. Hereinafter also). For example,
coupling agents constituted mainly from silane-based coupling
agents that contain silicon (Si), aluminum-based coupling agents
that contain aluminum (Al), titanium-based coupling agents that
contain titanium (Ti) and zirconium-based coupling agents that
contain zirconium (Zr) can be advantageously used.
[0050] A silane-based coupling agent can be, for example, a
compound in which one molecule is formed by a hydrophilic organic
functional group and a hydrophobic organic functional group being
bonded via silicon (Si). Examples of organic functional groups
include alkoxy groups (for example, alkoxy groups having 1 to 4
carbon atoms, typically methoxy groups and ethoxy groups), vinyl
groups, epoxy groups, styryl groups, methacrylic groups, acrylic
groups, amino groups, isocyanate groups, ureido groups, mercapto
groups and sulfide groups. A silane-based coupling agent having an
alkoxy group and an organic functional group other than an alkoxy
group in a single molecule is preferred. Of these, a silane-based
coupling agent having an alkoxy group and an epoxy group or amino
group in a single molecule is preferred.
[0051] Preferred examples of silane-based coupling agents include
epoxyalkoxysilanes such as 3-glycidoxypropyltrimethoxysilane,
3-glycidoxypropylmethyldiethoxysilane,
3-glycidoxypropyltriethoxysilane,
3-glycidoxypropylmethyldimethoxysilane and
2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; and
aminoalkoxysilanes such as 3-aminopropyltriethoxysilane,
3-aminopropyldimethylethoxysilane, 3-aminopropyltrimethoxysilane,
3-aminotriethoxysilane,
N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane.
N-2-(aminoethyl)-3-aminopropyltrimethoxysilane,
N-2-(aminoethyl)-3-aminopropyltriethoxyvsilane,
3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine,
N-phenyl-3-aminopropyltrimethoxysilane and
N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane
hydrochloride. Of these, 3-glycidoxypropyltriethoxysilane,
3-aminopropyltriethoxysilane and 3-aminopropyldimethylethoxysilane
are preferred, and 3-aminopropyltrimethoxysilane is particularly
preferred from perspectives such as further increasing the
mechanical strength of a lamination-shaped fired body.
[0052] Other examples of silane-based coupling agents include
vinylalkoxysilanes such as vinyltrichlorosilane,
vinyltrimethoxysilane and vinyltriethoxysilane; styrylalkoxysilanes
such as p-styryltrimethoxysilane; methacrylic alkoxysilanes such as
3-methacryloxypropylmethyldimethoxysilane,
3-methacryloxypropyltrimethoxysilane,
3-methacryloxypropylmethyldiethoxysilane and
3-methacryloxypropyltriethoxysilane; acrylic alkoxysilanes such as
3-acryloxypropyltrimethoxysilane: ureidoalkoxysilanes such as
3-ureidopropyltriethoxysilane; mercaptoalkoxysilanes such as
3-mercaptopropylmethyldimethoxysilane and
3-mercaptopropyltrimethoxysilane: sulfide alkoxysilanes such as
bis(triethoxysilylpropyl)tetrasulfide: isocyanate alkoxysilanes
such as 3-isocyanatopropyltriethoxysilane; isocyanurate
alkoxysilanes such as tris-(trimethoxysilylpropyl)isocyanurate;
3-chloropropyltrimethoxysilane, tetramethoxysilane,
tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane,
dimethyltriethoxysilane, phenyltriethoxysilane,
hexamethyldisilazane, hexyltrimethoxysilane, decyltrimethoxysilane,
butyltrichlorosilane, cyclohexyltrichlorosilane,
decyltrichlorosilane, dodecyltrichlorosilane, octyltrichlorosilane,
octadecyltrichlorosilane and tetradecyltrichlorosilane. It is
possible to use one of these silane-based coupling agents in
isolation, or a combination of two or more types thereof.
[0053] An aluminum-based coupling agent can be, for example, a
compound in which one molecule is formed by a hydrophilic organic
functional group and a hydrophobic organic functional group being
bonded via aluminum (Al). Preferred examples of aluminum-based
coupling agents include cyclic aluminum oxide octylate, cyclic
aluminum oxide isopropylate, cyclic aluminum oxide stearate,
acetoalkoxy aluminum diisopropylates, aluminum acetylacetonate,
aluminum trimethoxide, aluminum tris(acetylacetonate), aluminum
tris(ethylacetoacetate), aluminum
diisopropoxymonoethylacetoacetate, aluminum isopropylate,
mono-sec-butoxy aluminum diisopropylate, ethylacetoacetate aluminum
diisopropylate, alkylacetoacetate aluminum diisopropylates,
aluminum sec-butyrate, aluminum ethylate, aluminum
tris(ethylacetoacetate), aluminum
monoacetylacetonate-bis(ethylacetoacetate), aluminum
tris(acetylacetonate) and aluminum
monoisopropoxy-monooleoxyethylacetoacetate. Of these, cyclic
aluminum oxide octylate and acetoalkoxy aluminum diisopropylates
are preferred from perspectives such as further increasing the
mechanical strength of a lamination-shaped fired body. It is
possible to use one of these aluminum-based coupling agents in
isolation, or a combination of two or more types thereof.
[0054] A titanium-based coupling agent can be, for example, a
compound in which one molecule is formed by a hydrophilic organic
functional group and a hydrophobic organic functional group being
bonded via titanium (Ti). Preferred examples of titanium-based
coupling agents include tetraoctyl-bis(di-tridecylphosphite)
titanate, isopropyl-tris(dioctylpyrophosphate) titanate,
tetraisopropyl-bis(dioctylphosphite) titanate,
tetra(2,2-diallyloxymethyl)-bis(di-tridecyl)phosphite titanate,
bis(dioctylpyrophosphate)oxyacetate titanate,
bis(dioctylpyrophosphate)ethylene titanate, isopropyltriisostearoyl
titanate, isopropyltri-dodecylbenzenesulfonyl titanate,
isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl
titanate, isopropylisostearoyldiacrylic titanate,
isopropyl-tri(dioctylphosphate) titanate, isopropyltricumylphenyl
titanate, isopropyl-tri(N-aminoethyl.aminoethyl) titanate,
dicumylphenyloxyacetate titanate, diisostearoylethylene titanate,
isopropyltristearoyl titanate,
tetra(2,2-diallyloxymethyl-1-butyl)-bis(di-tridecylphosphite)
titanate, bis(dioctylpyrophosphate)diisopropyl titanate,
tetramethyl ortho-titanate, tetraethyl ortho-titanate, tetrapropyl
ortho-titanate, tetraisopropyltetraethyl ortho-titanate, tetrabutyl
ortho-titanate, butyl polytitanate, tetraisobutyl ortho-titanate,
2-ethylhexyl titanate and stearyl titanate. Of these,
tetraoctyl-bis(di-tridecylphosphite) titanate is preferred from
perspectives such as further increasing the mechanical strength of
a lamination-shaped fired body. It is possible to use one of these
titanium-based coupling agents in isolation, or a combination of
two or more types thereof.
[0055] A zirconium-based coupling agent can be, for example, a
compound in which one molecule is formed by a hydrophilic organic
functional group and a hydrophobic organic functional group being
bonded via zirconium (Zr). Preferred examples of zirconium-based
coupling agents include a 1-butanol solution of zirconium (IV)
butoxide, tetra-n-propoxy zirconium, tetra-butoxy zirconium,
zirconium tetraacetylacetonate, zirconium
dibutoxy-bis(acetylacetonate), zirconium
tributoxyethylacetoacetate, zirconium
butoxyacetylacetonate-bis(ethylacetoacetate), tetra-n-propoxy
zirconium, tetra-n-butoxy zirconium, zirconium
tributoxyacetylacetonate, zirconium tributoxystearate, zirconium
monobutoxyacetylacetonate-bis(ethylacetoacetate),
neoalkoxy-tris(neodecanoyl) zirconates,
neoalkoxy-tris(dodecyl)benzenesulfonyl zirconates,
neoalkoxy-tris(dioctyl)phosphate zirconates,
neoalkoxy-tris(dioctyl)pyrophosphate zirconates,
neoalkoxy-tris(ethylenediamino)ethyl zirconates,
neoalkoxy-tris(m-amino)phenyl zirconates,
tetra(2,2-diallyloxymethyl)butyl, di(di-tridecyl)phosphite
zirconate, neopentyl(diallyl)oxy, trineodecanoyl zirconate,
neopentyl(diallyl)oxy, tri(dodecyl)benzene-sulfonyl zirconate and
neopentyl(diallyl)oxy, tri(dioctyl)phosphite zirconate. Of these, a
1-butanol solution of zirconium (IV) butoxide is preferred from
perspectives such as further increasing the mechanical strength of
a lamination-shaped fired body. It is possible to use one of these
zirconium-based coupling agents in isolation, or a combination of
two or more types thereof.
[0056] The content of the coupling agent in the coupling liquid is
not particularly limited, but a content of 50 to 100 mass % is
typically suitable, and a content of 85 to 100 mass % is
preferred.
[0057] The coupling liquid disclosed here may contain a non-aqueous
solvent in addition to the coupling agent. The non-aqueous solvent
used in the coupling liquid should be able to disperse or dissolve
the coupling agents mentioned above and is not particularly
limited, and aromatic hydrocarbon solvents such as toluene and
xylene; aliphatic hydrocarbon solvents such as n-hexane and
n-pentane: ketone-based solvents such as acetone, methyl ethyl
ketone, methyl isobutyl ketone and cyclohexanone: ether-based
solvents such as dioxane, diethyl ether, isopropyl ether and
tetrahydrofuran: ester-based solvents such as ethyl acetate, butyl
acetate and isobutyl acetate: glycol ether ester-based solvents
such as ethylene glycol ethyl ether acetate, propylene glycol
methyl ether acetate, 3-methyl-3-methoxybutyl acetate and
ethyl-3-ethoxypropionate; and alcohol-based solvents such as
methanol, ethanol, 1-propanol, tert-butanol and 2-ethylhexanol can
be advantageously used as non-aqueous solvents. It is possible to
use one of these organic solvents in isolation, or a combination of
two or more types thereof. It is possible to use a coupling liquid
that contains substantially none of these organic solvents.
[0058] The method for impregnating the lamination-shaped article
with the coupling liquid that contains a coupling agent is not
particularly limited. For example, it is possible to use a method
of immersing the lamination-shaped article in the coupling liquid
so as to impregnate the lamination-shaped article with the coupling
liquid or a method of applying the coupling liquid to the
lamination-shaped article so as to impregnate the lamination-shaped
article with the coupling liquid. In cases where the
lamination-shaped article is immersed in the coupling liquid, the
immersion time should be a time by which the coupling liquid can
adequately penetrate into gaps between non-hydrating reaction raw
material particles, and this time is generally 30 to 600 seconds,
preferably 40 to 300 seconds, and more preferably 50 to 120
seconds. The lamination-shaped article is removed from the coupling
liquid, and may then be allowed to dry naturally before being
fired. The drying time is not particularly limited, but is
generally 1 to 10 hours, and preferably 2 to 5 hours.
[0059] Firing Step
[0060] In the firing step of step S30, a lamination-shaped fired
body is obtained by firing the lamination-shaped article after the
impregnation step. It is preferable to set the maximum firing
temperature to fall within the range 600.degree. C. to 1650.degree.
C. in an oxygen atmosphere. In this way, the coupling agent and
water-soluble adhesive resin impregnated in the lamination-shaped
article are removed through pyrolysis, and sintering of
non-hydrating reaction raw material particles occurs in an
effective manner via metal elements in the coupling agent.
Therefore, it is possible to produce a lamination-shaped fired body
having higher strength. It is preferable to carry out the firing at
a maximum firing temperature of not less than 1250.degree. C. (and
preferably 1300.degree. C. to 1500.degree. C., for example
1350.degree. C. to 1450.degree. C.). In addition, the firing time
(the firing time at the maximum firing temperature) should
generally be 1 to 10 hours (preferably 1.5 to 5 hours, and
particularly preferably 2 to 3 hours). If the firing time is too
short, insufficient sintering occurs, meaning that the mechanical
strength of the lamination-shaped fired body may deteriorate, but
if the firing time is too long, the mechanical strength improvement
effect tends to stagnate and the time required for production
increases, which is a disadvantage.
[0061] In a preferred aspect, the firing step is carried out by
increasing the temperature from room temperature to the maximum
firing temperature at a fixed ramp rate, holding at the maximum
firing temperature for a prescribed period of time, and then
decreasing the temperature to room temperature at a fixed ramp down
rate. The ramp rate is not particularly limited, but is generally
0.1 to 10.degree. C./min, and preferably 1 to 10.degree. C./min. In
addition, the ramp down rate is not particularly limited, but is
generally 0.1 to 50.degree. C./min, and preferably 1 to 10.degree.
C./min. By firing the lamination-shaped article using this type of
firing schedule, a lamination-shaped fired body having high
strength can be stably obtained. Production of a lamination-shaped
fired body according to the present embodiment is completed in this
way.
[0062] Lamination-Shaped Fired Body
[0063] The lamination-shaped fired body disclosed here is produced
by means of a shaping step of shaping a lamination-shaped article
using a lamination shaping powder that contains non-hydrating
reaction raw material particles, an impregnation step of
impregnating the lamination-shaped article with a coupling liquid
that contains a coupling agent and, following the impregnation
step, a firing step of firing the lamination-shaped article so as
to obtain a lamination-shaped fired body. As a result, the obtained
lamination-shaped fired body can have superior mechanical strength
to the prior art. Typically, the three-point bending strength of
the lamination-shaped fired body, as measured in accordance with
JIS R 1601, is not less than 0.5 MPa (for example 0.5 to 20 MPa),
preferably not less than 0.6 MPa, more preferably not less than 0.8
MPa, further preferably not less than 2 MPa, and particularly
preferably not less than 3 MPa (for example, not less than 5 MPa,
and typically not less than 8 MPa).
[0064] In the lamination-shaped fired body disclosed here, a metal
oxide is generated at a suitable temperature following pyrolysis of
metal elements in the coupling agent in the firing step. As a
result, a metal oxide derived from metal elements in the coupling
agent (for example, SiO.sub.2, Al.sub.2O.sub.3, TiO.sub.2 or
ZrO.sub.2) is present at grain boundaries between non-hydrating
reaction raw material particles that constitute the
lamination-shaped fired body. Preferred examples of the
lamination-shaped fired body disclosed here include a
lamination-shaped fired body in which the non-hydrating reaction
raw material particles contain at least one element selected from
among Al, Zr, Ti, Zn, Ni, Fe and Si and in which an oxide
containing at least one element selected from among Si, Ti, Al and
Zr, other than those elements contained in the non-hydrating
reaction raw material particles, is present at grain boundaries
between non-hydrating reaction raw material particles; a
lamination-shaped fired body in which the non-hydrating reaction
raw material particles contain Al and in which an oxide containing
at least one element selected from among Si, Ti and Zr is present
at grain boundaries between non-hydrating reaction raw material
particles; a lamination-shaped fired body in which the
non-hydrating reaction raw material particles contain Zr and in
which an oxide containing at least one element selected from among
Si, Al and Ti is present at grain boundaries between non-hydrating
reaction raw material particles; a lamination-shaped fired body in
which the non-hydrating reaction raw material particles contain Si
and in which an oxide containing at least one element selected from
among Ti, Al and Zr is present at grain boundaries between
non-hydrating reaction raw material particles; and a
lamination-shaped fired body in which the non-hydrating reaction
raw material particles contain Ti and in which an oxide containing
at least one element selected from among Si, Al and Zr is present
at grain boundaries between non-hydrating reaction raw material
particles. As a result of a metal oxide derived from metal elements
contained in the coupling agent being present at grain boundaries
between non-hydrating reaction raw material particles, it is
possible to achieve a high strength lamination-shaped fired body,
which could not be obtained in the past. Moreover, the presence of
a metal oxide derived from metal elements contained in the coupling
agent at grain boundaries between non-hydrating reaction raw
material particles can be confirmed by elemental analysis carried
out by, for example, an energy dispersion type X-ray spectroscopy
method (EDX, for example SEM-EDX).
[0065] Kit for Producing Lamination-Shaped Fired Body
[0066] The invention disclosed here encompasses provision of, for
example, a kit able to be used to produce the lamination-shaped
fired body described above. That is, the invention disclosed here
provides a kit for producing a lamination-shaped fired body
obtained by firing a lamination-shaped article. This production kit
includes a lamination shaping powder that contains non-hydrating
reaction raw material particles, and a coupling liquid which
contains a coupling agent and which is impregnated in an unfired
lamination-shaped article that is shaped using the lamination
shaping powder. This production kit can be advantageously used in a
method for producing the lamination-shaped fired body disclosed
here. According to this production kit, a high quality
lamination-shaped fired body having superior mechanical strength to
the prior art can be produced.
[0067] Several working examples relating to the present invention
will now be explained, but the present invention is in no way
limited to these working examples.
[0068] A lamination shaping powder was prepared by weighing out
non-hydrating reaction raw material particles and PVA as
water-soluble adhesive particles at a mass ratio of 90:10 and
mixing for 30 seconds using a PolyMix. This lamination shaping
powder was introduced into a ProJet 460 Plus available from 3D
Systems, Inc., shaped into a lamination-shaped article (a test
piece) having a height of 4 mm, a width of 40 mm and a thickness of
3 mm, and allowed to dry for 16 hours at room temperature. In
addition, a coupling liquid containing a coupling agent was
prepared, and the shaped lamination-shaped article was immersed for
1 minute in the coupling liquid so as to impregnate the
lamination-shaped article with the coupling liquid. The
lamination-shaped article was then removed from the coupling liquid
and allowed to dry naturally for 3 hours on a paper towel. A
lamination-shaped fired body was then obtained by firing the
impregnated lamination-shaped article by increasing the temperature
to 1400.degree. C. at a ramp rate of 2.degree. C./min in an air
atmosphere, maintaining a temperature of 1400.degree. C. for 2
hours, and then reducing the temperature to room temperature at a
ramp down rate of 2.degree. C./min. The types of non-hydrating
reaction raw material particles and coupling agent used in the
lamination-shaped fired bodies of the examples are shown in Tables
1 and 2. Moreover, for purposes of comparison, lamination-shaped
articles were fired without being impregnated with a coupling
liquid in Comparative Examples 1 and 2.
TABLE-US-00001 TABLE 1 Non-hydrating reaction raw Strength material
particles Coupling agent (MPa) Working Alumina
3-aminopropyltriethoxy- 8.41 Example 1 silane Working Alumina
3-aminopropyldimethyl- 2.14 Example 2 ethoxysilane Working Alumina
3-glycidoxypropyltri- 5.26 Example 3 ethoxysilane Working Alumina
60% petroleum solution 0.9 Example 4 of cyclic aluminum oxide
octylate Working Alumina Acetoalkoxy aluminum 0.68 Example 5
diisopropylate Working Alumina Tetraoctyl-bis(di-tridecyl- 3.33
Example 6 phosphite) titanate Working Alumina 85% 1-butanol
solution 0.69 Example 7 of zirconium (IV) butoxide Comparative
Alumina None 0.41 Example 1
TABLE-US-00002 TABLE 2 Non-hydrating reaction raw Strength material
particles Coupling agent (MPa) Working Zirconia
3-aminopropyltriethoxy- 2.11 Example 8 silane Working Zirconia
Acetoalkoxy aluminum 0.88 Example 9 diisopropylate Working Zirconia
Tetraoctyl-bis(di-tridecyl- 0.61 Example 10 phosphite) titanate
Comparative Zirconia None 0.34 Example 2
[0069] The three-point bending strength (crushing strength) of the
lamination-shaped fired bodies obtained in the examples was
measured using a method according to JIS R 1601. The results are
shown in the "Strength (MPa)" column in Tables 1 and 2.
[0070] As shown in Table 1, the lamination-shaped fired bodies of
Working Examples 1 to 7, which were obtained by impregnating a
lamination-shaped article with a coupling liquid and then firing,
achieved better results in terms of three-point bending strength
than Comparative Example 1, which was obtained by firing a
lamination-shaped article without impregnating a coupling liquid.
From these results, it can be confirmed that a lamination-shaped
fired body having excellent mechanical strength can be obtained by
impregnating a lamination-shaped article with a coupling liquid and
then firing. In the case of the lamination-shaped fired bodies
tested here, Working Examples 1 to 3, which were obtained using a
silane-based coupling agent, achieved better results in terms of
three-point bending strength than Working Examples 4 to 5 and 7,
which were obtained using other coupling agents.
[0071] Moreover, the lamination-shaped fired bodies of Working
Examples 8 to 10, which were obtained using zirconia instead of
alumina, like the lamination-shaped fired bodies of Working
Examples 1 to 7, which were obtained using alumina, achieved better
results in terms of three-point bending strength than Comparative
Example 2, which was obtained by firing a lamination-shaped article
without impregnating a coupling liquid. From these results, it was
confirmed that a performance improvement effect (a mechanical
strength improvement effect) achieved by impregnating a
lamination-shaped article with a coupling liquid and then firing
was achieved regardless of the type of non-hydrating reaction raw
material particles used.
[0072] Specific examples of the present invention have been
explained in detail above, but these are merely examples, and do
not limit the scope of the invention. The features described in the
claims can include aspects obtained by variously modifying or
altering the specific examples shown above.
* * * * *